JP6946792B2 - Coloring composition, cured product, and image display device - Google Patents

Description

The present invention resides in colored compositions, cured products, and image display devices.

Flat panel displays such as liquid crystal displays and organic EL (Electroluminescence) display devices are widely used, and color filters are used in these displays. In keeping with the trend of energy saving, color filters are required to have higher color purity, higher brightness, and higher contrast.
So far, a coloring composition using a pigment has been mainly used as a material for forming a color filter. However, in order to obtain high brightness and high contrast, for example, in Non-Patent Document 1, the particle size of pigment particles is set. A method of finely dispersing to 1/2 or less of the coloration wavelength is disclosed.

On the other hand, as a method for obtaining a high-luminance coloring composition, it is known that in addition to the conventional pigment, another colorant exhibiting high brightness is blended in an arbitrary ratio. For example, Patent Documents 1 to 3 disclose a coloring composition containing a pigment and a triarylmethane-based compound as a coloring material.

International Publication No. 2012/129318 Pamphlet Japanese Unexamined Patent Publication No. 2014-012814 Japanese Unexamined Patent Publication No. 2012-083652

Kiyoto Hashizume, "Journal of the Japan Society of Color Material", December 1967, p608

However, in the method described in Non-Patent Document 1, since the blue pigment in particular has a shorter coloration wavelength than other red and green pigments, further fine dispersion is required in this case, which increases the cost and stabilizes after dispersion. Gender matters.
Further, according to the study by the present inventors, in the coloring compositions described in Patent Documents 1 to 3, the absorbance at the absorption maximum of the triarylmethane-based compound contained therein at the time of firing at 230 ° C. in the color filter manufacturing process. It was found that the heat resistance was not sufficient due to the large decrease in heat resistance.

Therefore, it is an object of the present invention to provide a coloring composition which can significantly suppress a decrease in absorbance due to heating and has sufficient heat resistance in a color filter manufacturing process.

As a result of diligent studies by the present inventors, it has been found that the above-mentioned problems can be solved by containing a specific dispersant as a dispersant contained in the coloring composition, and the present invention has been completed.
That is, the gist of the present invention is as follows.

[1] A coloring composition containing (a) a colorant, (b) a dispersant, and (c) a solvent.
The colorant (a) contains a triarylmethane-based compound and contains.
A coloring composition, wherein the dispersant (b) contains a dispersant (b1) having an adsorbing group containing an aromatic heterocycle.
[2] The coloring composition according to claim 1, wherein the aromatic heterocycle contained in the adsorbing group of the dispersant (b1) is an imidazole ring, a pyridine ring, or a carbazole ring.

[3] The coloring composition according to [1] or [2], wherein the triarylmethane compound is a compound represented by the following general formula (I).

(In formula (I), R ^{1 to} R ⁴ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
Ar represents a monovalent aromatic ring group which may have a substituent.
n represents 0 or 1, and when it is 0, there is no bond.
X represents an a-valent linking group.
A ^c- represents a c-valent anion.
a, b, c, and d represent integers 1 to 4, and satisfy the relationship of a × b = c × d.
m represents 0 or 1. When m is 0, there is no bond and a is 1. )

[4] The coloring composition according to any one of [1] to [3], wherein the colorant (a) further contains a pigment.
[5] The coloring composition according to any one of [1] to [4], which further contains (d) a binder resin.
[6] The coloring composition according to any one of [1] to [5], which further contains (e) a photopolymerizable monomer and (f) a photopolymerization initiator.

[7] A cured product composed of the coloring composition according to any one of [1] to [6].
[8] An image display device having the cured product according to [7].

According to the present invention, it is possible to provide a coloring composition which can significantly suppress a decrease in absorbance due to heating and has sufficient heat resistance in a color filter manufacturing process.

FIG. 1 is a schematic cross-sectional view showing an example of an organic EL device having the color filter of the present invention.

Embodiments of the present invention will be described in detail below, but the following description is an example of embodiments of the present invention, and the present invention is not limited to these contents.
In the present invention, "(meth) acrylic", "(meth) acrylate" and the like mean "at least one of acrylic and methacrylic", "at least one of acrylate and methacrylate" and the like, for example, "( "Meta) acrylic acid" shall mean "at least one of acrylic acid and methacrylic acid".

Further, the "total solid content" shall mean all the components other than the solvent contained in the coloring composition of the present invention.
Further, the "aromatic ring" shall mean both an "aromatic hydrocarbon ring" and an "aromatic heterocycle".
In addition, terms such as "CI pigment green" mean the names of color materials contained in the Color Index (CI).

The coloring composition of the present invention contains (a) a colorant, (b) a dispersant, and (c) a solvent, and the (a) colorant contains a triarylmethane compound, and the (b) dispersant. However, it contains a dispersant (b1) having an adsorbing group containing an aromatic heterocycle. Further, it is preferable to contain (d) a binder resin, (e) a photopolymerizable monomer, and (f) a photopolymerization initiator, and other components may be contained if necessary.

[(A) Colorant]
The coloring composition of the present invention contains (a) a coloring agent. A colorant is a component that colors a coloring composition. (A) By including a colorant, desired light absorption can be obtained. (A) As the colorant, a pigment or a dye may be used.

(Triarylmethane compound)
In the coloring composition of the present invention, (a) the coloring agent contains a triarylmethane-based compound. This is because triarylmethane compounds generally have a sharp absorption peak near the maximum absorption wavelength and have low absorption in other wavelength regions, and particularly in a blue coloring composition, the absorption of blue light around 450 nm is small. , It is considered that the obtained patterns such as blue pixels have high brightness.
The triarylmethane-based compound means a compound containing at least a triarylmethane structure. Aryl in triarylmethane means an aromatic ring group, and means an aromatic hydrocarbon ring group and an aromatic heterocyclic group. That is, the triarylmethane compound means a compound in which three aromatic ring groups are bonded at least with sp2 carbon. In addition, it may be further linked with a linking group other than sp2 carbon.

The number of carbon atoms of the aryl in the triarylmethane structure, that is, the aromatic ring group is not particularly limited, but is preferably 50 or less, more preferably 40 or less, further preferably 30 or less, particularly preferably 20 or less, and usually 4 or more. 6 or more is preferable, and 8 or more is more preferable. When it is set to the upper limit value or less, the absorption of the aromatic ring group itself tends to decrease and the brightness tends to be improved, and when it is set to the lower limit value or more, the durability after firing tends to be improved.

The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. Examples of the aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, and a triphenylene ring, which have one free atomic value. Examples include groups such as acenaphthene ring, fluoranthene ring, and fluorene ring.
Further, the aromatic heterocycle in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrazole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, and a carbazole ring having one free atomic value. Ring, Pyrrolomidazole ring, Pyrrolopyrazole ring, Pyrrolopyrrole ring, Thienopyrol ring, Thienothiophene ring, Flopyrole ring, Flofran ring, Thienofuran ring, Benzisoxazole ring, Benzimidazole ring, Benzimidazole ring, Ppyridine ring, Pyrazine ring, Examples thereof include groups such as a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a sinoline ring, a quinoxaline ring, a phenanthridin ring, a benzimidazole ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring.

The aryl in the triarylmethane structure, that is, the aromatic ring group, may have a substituent. The substituents that the aryl group may have include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an amino group, a hydroxyl group, an alkoxyl group having 1 to 8 carbon atoms, an acetyloxy group and 2 to 9 carbon atoms. Alkylcarbonyloxy group, sulfonic acid group, sulfamoyl group, alkylsulfamoyl group having 2 to 9 carbon atoms, carbonyl group, alkylcarbonyl group having 2 to 9 carbon atoms, hydroxyethyl group, acetylamide group and the like. Among these, an amino group is preferable from the viewpoint of steepness of transmission spectrum and durability after firing. As a result, the transmission spectrum becomes steep, and the brightness before heating tends to be sufficiently high. The amino group may be any 1st to 3rd class amino group, and is preferably a secondary or tertiary amino group from the viewpoint of durability after firing.

Further, in the triarylmethane-based compound, from the viewpoint of durability after calcination, it is preferable that at least two of the three aromatic ring groups are linked by a linking group other than sp2 carbon, and they are linked by an oxygen atom. It is more preferable that it is.

Further, the present form of the triarylmethane compound in the coloring composition of the present invention is not particularly limited, and may be dissolved or dispersed. The triarylmethane compound may be a dye or a pigment.

On the other hand, from the viewpoint of durability after firing, the triarylmethane compound is preferably an intermolecular salt of a cation having a triarylmethane structure and an anion. The specific structure of the intermolecular salt is not particularly limited, but from the viewpoint of steepness of the transmission spectrum and durability after firing, the compound represented by the following general formula (I) is preferable.

In formula (I), R ^{1 to} R ⁴ independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
Ar represents a monovalent aromatic ring group which may have a substituent.
n represents 0 or 1, and when it is 0, there is no bond.
X represents an a-valent linking group.
A ^c- represents a c-valent anion.
a, b, c, and d represent integers 1 to 4, and satisfy the relationship of a × b = c × d.
m represents 0 or 1. When m is 0, there is no bond and a is 1.

(R ^{1 to} R ⁴ )
In the formula (I), R ^{1 to} R ⁴ independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
Examples of the alkyl group include a linear, branched or cyclic alkyl group, and a group in which these are bonded. The number of carbon atoms is preferably 1 or more, more preferably 2 or more, preferably 10 or less, more preferably 6 or less, still more preferably 4 or less. When it is set to the lower limit value or more, the durability after firing tends to be improved, and when it is set to the upper limit value or less, the influence of the rotation inhibition of the aryl in the triarylmethane structure due to steric hindrance is suppressed. The steepness of the transmission spectrum tends to improve.

Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, 2-propyl group, n-butyl group, isobutyl group, tert-butyl group, cyclohexyl group, cyclohexylmethyl group, cyclohexylethyl group, 3-. Examples include a methylbutyl group. Among these, a linear alkyl group is preferable from the viewpoint of yield in the synthetic process of the triarylmethane compound.
Specific examples of the alkyl group having a substituent include a phenethyl group, a 2-ethoxyethyl group, a 4,4,4-trifluorobutyl group and the like.

Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms is preferably 6 or more, preferably 18 or less, more preferably 14 or less, still more preferably 10 or less. When it is set to the lower limit value or more, the durability at the time of firing tends to be improved, and when it is set to the upper limit value or less, the influence of the rotation inhibition of the aryl in the triarylmethane structure due to steric hindrance is suppressed. The steepness of the transmission spectrum tends to improve.

The ring of the aromatic hydrocarbon ring group may be a monocyclic ring or a fused ring, for example, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, which have one free valence. Examples thereof include groups such as a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.
Further, the ring contained in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrazole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, and a carbazole ring having one free atomic value. Ring, Pyrrolomidazole ring, Pyrrolopyrazole ring, Pyrrolopyrrole ring, Thienopyrol ring, Thienothiophene ring, Flopyrole ring, Flofran ring, Thienofuran ring, Benzisoxazole ring, Benzimidazole ring, Benzimidazole ring, Ppyridine ring, Pyrazine ring, Examples thereof include groups such as a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a sinoline ring, a quinoxaline ring, a phenanthridin ring, a benzimidazole ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring.

Among these, from the viewpoints of durability after firing, steepness of transmission spectrum, and light resistance, R ^{1 to} R ⁴ each independently have an alkyl group or a substituent which may have a substituent. It is preferable that it is an aromatic ring group, and R ¹ and R ² are alkyl groups which may independently have a substituent, and R ³ and R ⁴ may have a substituent. More preferably, it is a good aromatic ring group.

(Ar)
In the formula (I), Ar represents a monovalent aromatic ring group which may have a substituent.
Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms is preferably 6 or more, preferably 18 or less, more preferably 14 or less, still more preferably 10 or less. When it is set to the lower limit value or more, the durability at the time of firing tends to be improved, and when it is set to the upper limit value or less, the influence of the rotation inhibition of the aryl in the triarylmethane structure due to steric hindrance is suppressed. The steepness of the transmission spectrum tends to improve.

The ring of the aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. Examples of the aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, and a triphenylene ring, which have one free atomic value. Examples include groups such as acenaphthene ring, fluoranthene ring, and fluorene ring.
Further, the ring contained in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrazole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, and a carbazole ring having one free atomic value. Ring, Pyrrolomidazole ring, Pyrrolopyrazole ring, Pyrrolopyrol ring, Thienopyrol ring, Thienothiophene ring, Flopyrole ring, Flofuran ring, Thienofranc ring, Benzisoxazole ring, Benzimidazole ring, Benzimidazole ring, pyridine ring, Pyrazine ring, Examples thereof include groups such as a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a sinoline ring, a quinoxaline ring, a phenanthridin ring, a benzimidazole ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring.

Among these, when n is 1, Ar has a substituent from the viewpoint of making the color tone reddish purple to purple, and reducing the absorption around 450 nm to improve the brightness, especially in the blue coloring composition. It is preferably a phenyl group which may be used. On the other hand, when n is 0, Ar may have a substituent, especially from the viewpoint of making the color tone blue in the blue coloring composition and reducing the absorption near 450 nm to improve the brightness. Alternatively, it is preferably a thiazolyl group which may have a substituent.

(N)
In the formula (I), n represents 0 or 1, and when it is 0, there is no bond.
In particular, in the blue coloring composition, it is preferable that n is 0 from the viewpoint of reducing the absorption around 450 nm to improve the brightness or making the color tone blue, while improving the durability after firing. From the viewpoint of setting the color tone from magenta to purple, n is preferably 1.

(X)
In the formula (I), X represents an a-valent linking group. The a-valent linking group represents an a-valent hydrocarbon group, an interrupted a-valent hydrocarbon group, and a substituted a-valent hydrocarbon group.

Examples of the a-valent hydrocarbon group include linear, branched, cyclic, and combinations thereof. The number of carbon atoms is preferably 1 or more, more preferably 6 or more, further preferably 15 or more, still preferably 50 or less, more preferably 30 or less, still more preferably 20 or less. When it is at least the above lower limit value, the durability after firing tends to be improved, and when it is at least the above upper limit value, the solubility in a solvent tends to be improved.

Specific examples of the a-valent hydrocarbon group include a methylene group, an ethylene group, a propylene group, a butene group, a pentene group, a hexene group, a 2,2-dimethylpropylene group and 3,3- as those having an a of 2. Dimethylpentene group, divalent cyclopentane, divalent cyclohexane, divalent norbornan group, phenylene group, naphthylene group, divalent fluorene ring group, divalent indol ring group, divalent anthracene ring group, divalent Examples thereof include a furan ring group, a divalent thiophene ring group, and a combination thereof.

Examples of those having a a of 3 include a methine group, a trivalent cyclopentane ring group, a trivalent cyclohexane ring group, a trivalent benzene ring group, a trivalent naphthalene ring group, a trivalent triazine ring group, and these. Examples thereof include a combination of a trivalent hydrocarbon group and a divalent group having a of 2 above.

When a is 4, a tetravalent carbon atom, a tetravalent cyclopentane ring group, a tetravalent cyclohexane ring group, a tetravalent benzene ring group, a tetravalent naphthalene ring group, and these tetravalent hydrocarbons are used. A combination of a hydrogen group and a divalent group represented by the above a of 2, a combination of two trivalent groups of the above a of 3, or a combination of the above a of 3 Examples thereof include those in which two trivalent groups shown in the above are linked by the divalent group shown in the case where a is 2.

As the interrupted a-valent hydrocarbon groups, the carbon-carbon bonds contained in these a-valent hydrocarbon groups are represented by −O−, −CO−, −COO−, −CONH−, −CONR ^5−,. It may be interrupted by at least one selected from the group consisting of −NH −, −NR ⁵⁻ , −SO ₂₋ , −SO ₂ NH−, −SO ₂ NR ^{5−, −S−.}

Examples of R ⁵ include an alkyl group which may have a substituent and an aromatic ring group which may have a substituent. Among these, an alkyl group which may have a substituent is preferable from the viewpoint of synthesis.
Examples ^{of the alkyl group in R 5} include linear, branched or cyclic alkyl groups. The carbon number is usually 1 or more, preferably 2 or more, preferably 12 or less, more preferably 6 or less, still more preferably 3 or less. When it is set to the lower limit value or more, the durability tends to be high, and when it is set to the upper limit value or less, the synthesis tends to be easy.

Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, 2-propyl group, n-butyl group, isobutyl group, tert-butyl group, 2-ethylhexyl group, cyclohexyl group, cyclohexylmethyl group and cyclohexyl. Ethyl group, 3-methylbutyl group and the like can be mentioned. Among these, an ethyl group is preferable from the viewpoint of durability and synthesis.
The alkyl group may be substituted with the substituent described in the substituent group W1 described later.

Examples of the aromatic ring group in R ⁵ include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The carbon number is usually 4 or more, preferably 6 or more, and preferably 12 or less. When it is set to the lower limit value or more, the durability tends to be high, and when it is set to the upper limit value or less, the synthesis tends to be easy.

The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. Examples of the aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, and a triphenylene ring, which have one free atomic value. Examples include groups such as acenaphthene ring, fluoranthene ring, and fluorene ring.
Further, the aromatic heterocycle in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrazole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, and a carbazole ring having one free atomic value. Ring, Pyrrolomidazole ring, Pyrrolopyrazole ring, Pyrrolopyrrole ring, Thienopyrol ring, Thienothiophene ring, Flopyrole ring, Flofran ring, Thienofuran ring, Benzisoxazole ring, Benzimidazole ring, Benzimidazole ring, Ppyridine ring, Pyrazine ring, Examples thereof include groups such as a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a sinoline ring, a quinoxaline ring, a phenanthridin ring, a benzimidazole ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring. Among these, from the viewpoint of durability and synthesis, a benzene ring or a naphthalene ring having one free valence is preferable, and a benzene ring having one free valence is more preferable.

Examples of the substituent that the aromatic ring group may have include those described in the substituent group W2 described later.

Examples of the substituted a-valent hydrocarbon group include those in which the methine group contained in the trivalent or tetravalent hydrocarbon group is substituted with the following group among these a-valent hydrocarbon groups. .. * Indicates a bond.

In addition, among these a-valent hydrocarbon groups, the tetravalent carbon atom contained in the tetravalent hydrocarbon group may be substituted with the following group. However, * indicates a bond.

(A ^c- )
In the formula (I), ^Ac- represents a c-valent anion.
The c-valent anion is not particularly limited, for example ^{F -, Cl -, Br -} , I - , etc. halide ion;
_{(C 6 H 5) 4 B} -, (C 6 F 5) 4 B - like boron anion;
_{^{CH 3 COO -, C 2 H}} 5 COO -, C 6 H 5 COO - carboxylic acids such as anion;
SO ₄ ^2-, HSO ₄ ^-, etc. sulfate anion;
Phosphate anions such as HPO ₄ ^2- and PO ₄ ^3-;
Examples thereof include sulfonic acid anions.
Examples of the sulfonic acid anion include an aliphatic sulfonic acid anion which may have a substituent such as trifluoromethanesulfonic acid, methanesulfonic acid, pentansulfonic acid, hexanesulfonic acid, heptanesulfonic acid, dodecanesulfonic acid, and camphorsulfonic acid. ;
Aromatic sulfonic acid anion which may have a substituent such as benzenesulfonic acid, p-toluenesulfonic acid, 1-naphthalenesulfonic acid, 2-naphthalenesulfonic acid;
acid blue 80 (CI 61585), acid green 25 (CI 61570), acid blue 45 (CI 63010), acid blue 43 (CI 63000), acid blue 25 (C.I. 63000). I.62055), an anthraquinone dye anion having a sulfonate group such as acid blue 40 (CI65125);
Anions of phthalocyanine pigments having sulfonate groups such as direct blue 86 (CI 74810) and direct blue 199 (CI 14190);
Anion of indigo dye having a sulfonato group such as acid blue 74 (CI 73015);
Examples thereof include a halogenoalkylsulfonylimide anion and a halogenoalkylsulfonylmethide anion.

Among these, from the viewpoint of heat resistance, a halogenoalkylsulfonylimide anion which may have a substituent, a halogenoalkylsulfonylmethide anion which may have a substituent, (C ₆ F ₅ ) ₄ B ^- etc. Is preferable.

(A, b, c, d and m)
a, b, c, and d represent integers 1 to 4, and satisfy the relationship of a × b = c × d. m represents 0 or 1. When m is 0, there is no bond and a is 1.
Among these, it is preferable that a, b, c and d are 1 and m is 0 from the viewpoint of solubility in a solvent, durability after firing, and cost in the process of synthesizing a triarylmethane compound. On the other hand, from the viewpoint of solvent resistance after firing, electrical reliability, and suppression of dye transfer to adjacent pixels, a is 2, b and c are 1, d is 2, and m is 1. It is preferable to have.

Examples of the substituents that the alkyl groups in R ^{1 to} R ⁴ and X may have include those of the following substituent group W1. Further ^{, examples of the substituents that the aromatic ring groups in R 1 to} R ⁴ and Ar may have include those of the following substituent group W2.

(Substituent group W1)
Fluorine atom, chlorine atom, alkenyl group having 2 to 8 carbon atoms, alkoxyl group having 1 to 8 carbon atoms, phenyl group, mesityl group, tolyl group, naphthyl group, cyano group, acetyloxy group, alkyl having 2 to 9 carbon atoms A carbonyloxy group, a sulfamoyl group, an alkylsulfamoyl group having 2 to 9 carbon atoms, an alkylcarbonyl group having 2 to 9 carbon atoms, a phenethyl group, a hydroxyethyl group, an acetylamide group, and an alkyl group having 1 to 4 carbon atoms are bonded. A dialkylaminoethyl group, a trifluoromethyl group, a trialkylsilyl group having 1 to 8 carbon atoms, a nitro group, and an alkylthio group having 1 to 8 carbon atoms.
Among them, an alkoxyl group having 1 to 8 carbon atoms, a cyano group, an acetyloxy group, an alkylcarboxyl group having 2 to 8 carbon atoms, a sulfamoyl group, an alkylsulfamoyl group having 2 to 9 carbon atoms, and a fluorine atom are preferable. ..

(Substituent group W2)
Fluorine atom, chlorine atom, alkyl group with 1 to 8 carbon atoms, alkenyl group with 2 to 8 carbon atoms, alkoxyl group with 1 to 8 carbon atoms, phenyl group, mesityl group, trill group, naphthyl group, cyano group, acetyloxy Group, alkylcarbonyloxy group with 2-9 carbon atoms, sulfamoyl group, alkylsulfamoyl group with 2-9 carbon atoms, alkylcarbonyl group with 2-9 carbon atoms, hydroxyethyl group, acetylamide group, 1-carbon group A dialkylaminoethyl group, a trifluoromethyl group, a trialkylsilyl group having 1 to 8 carbon atoms, a nitro group, and an alkylthio group having 1 to 8 carbon atoms, which are formed by bonding 4 alkyl groups.
Among them, preferably an alkyl group having 1 to 12 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, a cyano group, an acetyloxy group, an alkylcarboxyl group having 2 to 8 carbon atoms, a sulfamoyl group, and an alkylsul having 2 to 9 carbon atoms. It is a famoyl group and a fluorine atom.

Among the compounds represented by the general formula (1), the compound represented by the following general formula (I-1) is preferable from the viewpoint of durability after firing and steepness of the transmission spectrum.

In formula (I-1), R ^{1 to} R ⁴ , Ar and X are synonymous with those in formula (I).
a', c and d represent integers 1 to 4, and satisfy the relationship of a'= c × d.
m represents 0 or 1. When m is 0, there is no bond.
D ^c- represents a c-valent halogenoalkylsulfonylimide anion or halogenoalkylsulfonylmethide anion that may have a substituent.

(A', c, d and m)
a', c, and d represent integers 1 to 4, and satisfy the relationship of a'= c × d. m represents 0 or 1. When m is 0, there is no bond.
Among these, it is preferable that a', c and d are 1 and m is 0 from the viewpoint of solubility in a solvent, durability after firing, and cost in the process of synthesizing a triarylmethane compound. On the other hand, from the viewpoints of solvent resistance after firing, electrical reliability, and suppression of dye transfer to adjacent pixels, a'is 2, c is 1, d is 2, and m is 1. Is preferable.

(D ^c- )
In the formula (I-1), D ^c- represents a c-valent halogenoalkylsulfonylimide anion or a halogenoalkylsulfonylmethide anion which may have a substituent.
The number of carbon atoms of the halogenoalkyl group in the halogenoalkylsulfonylimide anion or the halogenoalkylsulfonylmethide anion is preferably 12 or less, more preferably 10 or less, further preferably 6 or less, and usually 1 or more. be. When it is set to the lower limit value or more, the charge of the anion tends to be dispersed and the anion tends to be stabilized. Tends to be possible.

The type of halogen atom contained in the halogenoalkyl group is not particularly limited, but is preferably fluorine, chlorine, bromine, or iodine, more preferably fluorine or chlorine, and even more preferably fluorine. By setting the type of halogen atom to the above, the charge of the anion tends to be more delocalized and the heat resistance of the coloring material can be improved.
The number of halogen atoms contained in the halogenoalkyl group is not particularly limited, but is preferably 27 or less, more preferably 12 or less, further preferably 6 or less, and usually 3 or more. When it is set to the lower limit value or more, the charge of the anion tends to be dispersed and the anion tends to be stabilized, and when it is set to the upper limit value or less, it has appropriate solubility and is affected by the steric repulsion with the cation. Tends to be smaller, allowing for stronger interaction with cations.

Specific examples of the halogenoalkylsulfonylimide anion include bistrifluoromethanesulfonylimide anion, bispentafluoroethanesulfonylimide anion, and bisnonafluorobutanesulfonylimide anion. From the viewpoint of anion heat resistance, bistrifluoro A methanesulfonylimide anion or a bispentafluoroethanesulfonylimide anion is preferred, with a more preferred bistrifluoromethanesulfonylimide anion.

Specific examples of the halogenoalkylsulfonylmethide anion include tristrifluoromethanesulfonylimide anion, trispentafluoroethanesulfonylimide anion, and trisnonafluorobutanesulfonylimide anion, which are affected by steric repulsion with the cation. From the viewpoint of small size, tristrifluoromethanesulfonylimide anion or trispentafluoroethanesulfonylimide anion is preferable, and bistrifluoromethanesulfonylimide anion is more preferable.

Further, the substituent which the halogenoalkylsulfonylimide anion or the halogenoalkylsulfonylmethide anion may have is not particularly limited, but those exemplified as the above-mentioned substituent group W2 can be used, and among them, the anion. From the viewpoint of the stability of the charge distribution inside, an aromatic ring group which may have a substituent is preferable.
Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The carbon number is not particularly limited, but is preferably 30 or less, more preferably 12 or less, usually 4 or more, and preferably 6 or more. By setting the value to the upper limit or less, there is a tendency that steric hindrance with the cation can be suppressed and the anion can be stabilized.
The ring contained in the aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. Examples of the aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, and a triphenylene ring, which have one free atomic value. Examples include groups such as acenaphthene ring, fluoranthene ring, and fluorene ring.
Further, the ring contained in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the reported group heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrazole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, and a carbazole ring having one free atomic value. Ring, Pyrrolomidazole ring, Pyrrolopyrazole ring, Pyrrolopyrrole ring, Thienopyrol ring, Thienothiophene ring, Flopyrole ring, Flofran ring, Thienofuran ring, Benzisoxazole ring, Benzimidazole ring, Benzimidazole ring, Pyridine ring, Pyrazine ring, Examples thereof include groups such as a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinolin ring, a sinoline ring, a quinoxaline ring, a phenanthridine ring, a benzimidazole ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring.

Among these, from the viewpoint of suppressing steric damage with cations, a benzene ring, a naphthalene ring, a thiophene ring, or a triazine ring having a monovalent free valence is preferable, a benzene ring or a triazine ring is more preferable, and a triazine ring is preferable. More preferred. Since the triazine ring has high flatness, it is considered that the interaction with the aryl moiety of the cation of the triarylmethane compound and the anion moiety existing in the same system tends to be strong. Further, since it has a sulfonylimide skeleton or a sulfonylmethide skeleton, it is considered that there is little steric repulsion with the cation and it is easy to form a stronger ion pair. As a result, since the cation and the anion are difficult to separate, the heat resistance is high, the decrease in the interaction between the cation and the anion is easily suppressed even in an electric field, and the voltage retention rate of the obtained pixel tends to be high. There is.
The number of substituents that the halogenoalkylsulfonylimide anion or the halogenoalkylsulfonylmethide anion may have is not particularly limited, but is preferably 1 to 3 from the viewpoint of suppressing steric hindrance. Is more preferable.

(Anions represented by formulas (D-1) and (D-2))
Among these, from the viewpoint of anion stabilization, the substituent is preferably located at the end of the anion, and in particular, a monovalent anion represented by the following formula (D-1) or a following formula (D-2). It is preferably a monovalent anion represented.

In the above formula (D-1), R ^1a and R ^2a independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent. ..
R ^3a represents a direct bond, an alkylene group which may have a substituent, or a divalent aromatic ring group which may have a substituent.
R ^4a represents a halogenoalkyl group.
X ^{1 to} X ³ are each independently bonded, _{at least one group selected from the group consisting of-(CH 2} )-, -NH-, -O- and -S-, or a group in which two or more of these are bonded. Represents.

In the above formula (D-2), R ^5a and R ^6a independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent. ..
R ^7a represents a direct bond, an alkylene group which may have a substituent, or a divalent aromatic ring group which may have a substituent.
R ^8a and R ^9a each independently represent a halogenoalkyl group.
X ^{4 to} X ⁶ are each independently bonded, _{at least one group selected from the group consisting of-(CH 2} )-, -NH-, -O- and -S-, or a group in which two or more of these are bonded. Represents.

(R ^1a , R ^2a , R ^5a , R ^6a )
R ^1a , R ^2a , R ^5a , and R ^6a each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
Among these, examples of the alkyl group include a linear, branched or cyclic alkyl group, and a group in which these are linked. The carbon number is preferably 8 or less, more preferably 5 or less, and preferably 2 or more, from the viewpoint of solubility in a solvent.
Specific examples include methyl group, ethyl group, n-propyl group, 2-propyl group, n-butyl group, isobutyl group, tert-butyl group, 2-ethylhexyl group, cyclohexyl group, cyclohexylmethyl group, cyclohexylethyl group, Examples include 3-methylbutyl group. From the viewpoint of the balance between the crystallinity and the solubility of the salt formed in these, a linear or branched alkyl group is preferable, and a linear alkyl group is more preferable.
Examples of the substituent that the alkyl group may have include those of the above-mentioned substituent group W1.

Among these, examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The carbon number is preferably 30 or less, more preferably 12 or less, preferably 4 or more, and 6 or more, from the viewpoint of the balance between crystallinity and solubility, from the viewpoint of suppressing steric hindrance. More preferably.
The ring contained in the aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. Examples of the aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, and a triphenylene ring, which have one free atomic value. Examples include groups such as acenaphthene ring, fluoranthene ring, and fluorene ring.
Further, the ring contained in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrazole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, and a carbazole ring having one free atomic value. Ring, Pyrrolomidazole ring, Pyrrolopyrazole ring, Pyrrolopyrol ring, Thienopyrol ring, Thienothiophene ring, Flopyrole ring, Flofuran ring, Thienofranc ring, Benzisoxazole ring, Benzimidazole ring, Benzimidazole ring, pyridine ring, Pyrazine ring, Examples thereof include groups such as a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a sinoline ring, a quinoxaline ring, a phenanthridin ring, a benzimidazole ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring.
Among these aromatic ring groups, an aromatic hydrocarbon ring group is preferable from the viewpoint of ease of production.
Examples of the substituent that the aromatic ring group may have include those of the substituent group W2.

Among these, from the viewpoint of the stability of the coloring composition, R ^1a and R ^2a are each independently an alkyl group which may have a substituent or an aromatic ring group which may have a substituent. Is preferable.
R ^1a and R ^2a may be the same or different. For example, R ^1a and R ^2a may be alkyl groups which may each have an independent substituent, and R ^{1a and R 2a} may each have an independent substituent. It may be a ring group, R ^1a may be an alkyl group which may have a substituent, and R ^2a may be an aromatic ring group which may have a substituent.
R ^5a and R ^6a may be the same or different. For example, R ^5a and R ^6a may be alkyl groups which may each have an independent substituent, and R ^{5a and R 6a} may each have an independent substituent. It may be a ring group, R ^5a may be an alkyl group which may have a substituent, and R ^6a may be an aromatic ring group which may have a substituent.

(R ^3a , R ^7a )
R ^3a represents a direct bond, an alkylene group which may have a substituent, or a divalent aromatic ring group which may have a substituent.
Among these, examples of the alkylene group include a linear alkylene group, a branched chain alkylene group, a cyclic alkylene group, and a group in which these are bonded. The carbon number is preferably 8 or less, more preferably 5 or less, and usually 1 or more, from the viewpoint of suppressing charge bias.
Specific examples include a methylene group, an ethylene group, a propylene group and the like. Among these, a methylene group is preferable from the viewpoint of suppressing charge bias.
Examples of the substituent that the alkylene group may have include those of the substituent group W1.

Among these, examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group. From the viewpoint of anion rigidity and heat resistance, the carbon number is preferably 30 or less, more preferably 12 or less, and usually 4 or more, preferably 6 or more.
The ring contained in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. Examples of the aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, and a triphenylene ring, which have two free valences. Examples include groups such as acenaphthene ring, fluoranthene ring, and fluorene ring.
Further, the ring contained in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrazole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, and a carbazole ring having two free atomic valences. Ring, Pyrrolomidazole ring, Pyrrolopyrazole ring, Pyrrolopyrrole ring, Thienopyrol ring, Thienothiophene ring, Flopyrole ring, Flofran ring, Thienofuran ring, Benzisoxazole ring, Benzimidazole ring, Benzimidazole ring, Ppyridine ring, Pyrazine ring, Examples thereof include groups such as a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a sinoline ring, a quinoxaline ring, a phenanthridin ring, a benzimidazole ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring.
Among these divalent aromatic ring groups, a divalent aromatic hydrocarbon ring group is preferable, and a divalent benzene ring is more preferable, from the viewpoint of suppressing charge bias.
Examples of the substituent that the divalent aromatic ring group may have include those of the substituent group W2.

(R ^4a , R ^8a , R ^9a )
R ^4a , R ^8a , and R ^9a each independently represent a halogenoalkyl group.
The type of halogen atom contained in the halogenoalkyl group is not particularly limited, but is preferably fluorine, chlorine, bromine, or iodine, more preferably fluorine or chlorine, and even more preferably fluorine. By setting the type of halogen atom to the above, the charge of the anion tends to be more delocalized, and the heat resistance of the triarylmethane compound tends to be improved.
The number of halogen atoms contained in the halogenoalkyl group is not particularly limited, but is preferably 27 or less, more preferably 12 or less, further preferably 6 or less, and usually 3 or more. When it is set to the lower limit value or more, the charge of the anion tends to be dispersed and the anion tends to be stabilized, and when it is set to the upper limit value or less, it has appropriate solubility and is affected by the steric repulsion with the cation. Tends to be smaller, allowing for stronger interaction with cations.
The number of carbon atoms of the halogenoalkyl group is not particularly limited, but is preferably 12 or less, more preferably 6 or less, and usually 1 or more. When it is set to the lower limit value or more, the charge of the anion tends to be dispersed and the anion tends to be stabilized. Tends to be possible.
Specific examples thereof include a trifluoromethyl group, a pentafluoroethyl group, a 1,1,1-trifluoroethyl group, and the like, and a trifluoromethyl group is preferable from the viewpoint of suppressing charge bias.

(X ^{1 to} X ⁶ )
X ^{1 to} X ⁶ are each independently bonded, _{at least one group selected from the group consisting of-(CH 2} )-, -NH-, -O- and -S-, or a group in which two or more of these are bonded. Represents.
That is, X ^{1 to} X ⁶ may be independently bonded to two or more divalent groups selected from the above group, or may be bonded to two or more of one type. The number of pieces to be combined is usually 2 or more, usually 15 or less, preferably 12 or less, and more preferably 10 or less.
Among these, from the viewpoint of easiness of synthesis, − (CH ₂ ) − or −NH− is preferable, and −NH− is more preferable.

Among these anions, the heat resistance is high, and the influence of steric repulsion with the cation is small, so the interaction between the anion and the cation is large, the counterion is stabilized, and the heat resistance of the triarylmethane compound is improved. From the point of view, it can be a bistrifluoromethanesulfonylimide anion, a tristrifluoromethanesulfonylmethide anion, or a 2,6-diphenylamino-4-butylamino-1,3,5-triazine ring-containing trifluoromethanesulfonylimide anion. preferable.

On the other hand, among the compounds represented by the general formula (1), the compound represented by the following general formula (I-2) is preferable from the viewpoint of durability after firing.

In formula (I-2), R ^{1 to} R ⁴ are synonymous with those in formula (I).
a'', c and d represent integers 1 to 4, and satisfy the relationship of a'' = c × d.
E ^c- represents a c-valent halogenoalkylsulfonylimide anion or a halogenoalkylsulfonylmethide anion that may have a substituent.

(A'', c and d)
a'', c, and d represent integers 1 to 4, and satisfy the relationship of a'' = c × d.
Among these, a ″, c and d are preferably 1 from the viewpoint of solubility in a solvent, durability after firing, and cost in the process of synthesizing a triarylmethane compound.

(E ^c- )
In the formula (I-2), E ^c- represents a c-valent halogenoalkylsulfonylimide anion or a halogenoalkylsulfonylmethide anion which may have a substituent. As the c-valent halogenoalkylsulfonylimide anion or halogenoalkylsulfonylmethide anion which may have a substituent, the same ones listed as ^{D c- in the above (Formula I-1) are preferably used.} be able to.

(Molecular weight of triarylmethane compound)
The molecular weight of the triarylmethane compound is not particularly limited, but is preferably 300 or more, more preferably 1000 or more, further preferably 2000 or more, preferably 10,000 or less, more preferably 5000 or less, still more preferably 3000 or less. When it is at least the above lower limit value, the solvent resistance after firing, electrical reliability, and the ability to suppress dye transfer to adjacent pixels tend to be improved, and when it is at least the above upper limit value, the solubility in a solvent is improved. Durability after calcination and cost performance in the process of synthesizing triarylmethane compounds tend to be improved.

(Specific example of triarylmethane compound)
Specific examples of the cation moiety of the triarylmethane-based compound include the following.

Further, as a specific example of the cation portion of the triarylmethane-based compound, a combination of the cation structure shown below and a naphthalene ring compound described later can be mentioned.

The naphthalene ring compounds combined with the above cationic structure are shown below.

Specific examples of the anion moiety of the triarylmethane compound include the following.

(Method for synthesizing triarylmethane compounds)
The method for synthesizing triarylmethane compounds is not particularly limited, but for example, "Overview Synthetic Dyes" (Hiroshi Horiguchi, Sankyo Publishing, 1968), "Theoretical Manufacturing Dye Chemistry" (Yutaka Hosoda, Gihodo, 1957), International It can be synthesized according to the method described in Publication No. 2009/107734 and International Publication No. 2015/08217, but the method is not limited to this method.

(Content ratio of triarylmethane compound)
The colorant (a) in the coloring composition of the present invention contains a triarylmethane-based compound, but may contain one type of triarylmethane-based compound or may contain two or more types.
The content ratio of the triarylmethane compound in the coloring composition of the present invention is not particularly limited, but is preferably 3% by mass or more, more preferably 5% by mass or more, still more preferably 8% by mass or more, and further preferably 8% by mass or more in the total solid content. , 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less. When it is set to the lower limit value or more, the brightness tends to be high, and when it is set to the upper limit value or less, the durability after firing tends to be improved.

(Other colorants)
The (a) colorant in the color composition of the present invention contains a triarylmethane-based compound, but may further contain other colorants. Other colorants include other dyes and other pigments.

(Other dyes)
As other dyes, for example, azo dyes, anthraquinone dyes, phthalocyanine dyes, quinone imine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes, cyanine dyes, dipyrromethene dyes and the like are preferable. Can be mentioned.

Examples of the azo dye include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Disperse Thread 58, C.I. I. Disperse Blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Moldant Red 7, C.I. I. Moldant Yellow 5, C.I. I. Examples include Moldant Black 7.

Examples of the anthraquinone dye include C.I. I. Bat Blue 4, C.I. I. Acid Blue 25, C.I. I. Acid Blue 40, C.I. I. Acid Blue 80, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disperse Thread 60, C.I. I. Disperse Blue 56, C.I. I. Disperse blue 60 and the like can be mentioned.

In addition, as a phthalocyanine dye, for example, C.I. I. Direct Blue 86, C.I. I. Direct Blue 199, C.I. I. Batblue 5, JP-A-2002-14222, JP-A-2005-134759, JP-A-2010-191358, JP-A-2011-148950, etc. are examples of quinoneimine dyes such as C. .. I. Basic Blue 3, C.I. I. Basic Blue 9 and the like are used as quinoline dyes, for example, C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like can be used as nitro dyes, for example, C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 and the like can be mentioned.

Further, examples of the cyanine dye include those described in Pamphlet No. 2011/162217 of International Publication No. 2011/162217, and preferred embodiments are also the same.

Examples of the dipyrromethene dye include JP-A-2008-292970, JP-A-2010-84009, JP-A-2010-84141, JP-A-2010-85454, JP-A-2011-158654, and JP-A. Examples thereof include those described in Japanese Patent Application Laid-Open No. 2012-158739, Japanese Patent Application Laid-Open No. 2012-224852, Japanese Patent Application Laid-Open No. 2012-224489, Japanese Patent Application Laid-Open No. 2012-224847, and Japanese Patent Application Laid-Open No. 2012-224846.

The coloring composition of the present invention may contain only one type of other dye, or may contain two or more types of other dyes.

(Other pigments)
As other pigments, for example, when forming pixels of a color filter or the like, pigments of various colors such as blue and purple can be used. Examples of the chemical structure include organic pigments such as phthalocyanine, quinacridone, benzimidazolone, dioxazine, indanthrone, and perylene. In addition to this, various inorganic pigments and the like can also be used. Hereinafter, specific examples of pigments that can be used are shown by pigment numbers.

Examples of the blue pigment include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 and the like can be mentioned.

Among these, a phthalocyanine pigment having a central metal is preferable from the viewpoint of heat resistance and light resistance, and a blue copper phthalocyanine pigment is particularly preferable. Examples of the copper phthalocyanine pigment include C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, etc. are preferably mentioned, and most preferably C.I. I. Pigment Blue 15: 6.
Therefore, when the coloring composition of the present invention contains a blue pigment, 80% by mass or more, particularly 90% by mass or more, particularly 95 to 100% by mass, is C.I. I. Pigment Blue 15: 6 is preferred.

Examples of the purple pigment include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 and the like can be mentioned.
Among these, a purple dioxazine pigment is preferable, and C.I. I. Pigment Violet 19, 23 and the like are preferably mentioned, and more preferably C.I. I. Pigment Violet 23.

Therefore, when the coloring composition of the present invention contains a purple pigment, 80% by mass or more, particularly 90% by mass or more, particularly 95 to 100% by mass, is C.I. I. Pigment Violet 23 is preferred.
One of these may be used alone, or two or more thereof may be mixed and used in any combination and ratio.

The pigment that can be used in the coloring composition of the present invention preferably has a small average primary particle size from the viewpoint of forming pixels with high contrast, and specifically, the average primary particle size is 40 nm or less. It is preferably 35 nm or less, and more preferably 35 nm or less.
In particular, the blue copper phthalocyanine pigment also preferably has an average primary particle size of 40 nm or less, more preferably 35 nm or less, and further preferably 20 to 30 nm.

The average primary particle size of the dioxazine pigment is preferably 40 nm or less, more preferably 25 to 35 nm. From the viewpoint that the pigment is less likely to aggregate in the coloring composition, it is preferable that the average primary particle size is not too small.
Here, the average primary particle size of the pigment can be a value measured and calculated by the following method.

First, the pigment is ultrasonically dispersed in chloroform, dropped onto a collodion film-attached mesh, dried, and observed with a transmission electron microscope (TEM) to obtain a primary particle image of the pigment. From this image, the particle size of each of a plurality of (usually about 200 to 300) pigment particles is determined by setting the particle size of each pigment particle as the diameter equivalent to the area circle converted to the diameter of a circle having the same area.
Using the obtained primary particle size value, calculate the number average value according to the formula below to obtain the average particle size.

Grain size of individual pigment particles: X ₁ , X ₂ , X ₃ , X ₄ , ..., X _i , ... X _m (m is the number of particles)

Among the other colorants, it is preferable to contain other pigments from the viewpoint of improving heat resistance and light resistance, and more preferably to contain a blue pigment from the viewpoint of improving heat resistance and light resistance due to the blue color material.

When the coloring composition of the present invention contains other colorants, the content ratio thereof is not particularly limited, but is preferably 1% by mass or more, more preferably 3% by mass or more, and further preferably 5% by mass or more in the total solid content. It is preferable, 20% by mass or less is preferable, 15% by mass or less is more preferable, and 10% by mass or less is further preferable. When it is set to the lower limit value or more, the durability after firing tends to be improved, and when it is set to the upper limit value or less, the brightness tends to be improved.

[(B) Dispersant]
The coloring composition of the present invention contains (b) a dispersant. By including (b) a dispersant, (a) the colorant can be finely dispersed and the dispersed state thereof can be stabilized.
Further, the dispersant (b) in the coloring composition of the present invention contains a dispersant (b1) having an adsorbing group containing an aromatic heterocycle (hereinafter, abbreviated as "dispersant (b1)"). (B) By using the dispersant (b1) as the dispersant, the aromatic heterocycle contained therein is less likely to bond with the sp2 carbon of the triarylmethane compound even when heated, and the triarylmethane compound. It is considered that the conjugated system of the triarylmethane compound can be suppressed from collapsing and fading, and the decrease in the absorbance of the triarylmethane compound at the absorption maximum can be suppressed.

The number of rings contained in the aromatic heterocycle is not particularly limited, but is usually 1 or more, preferably 4 or less, more preferably 3 or less, still more preferably 2 or less. When the value is not more than the upper limit, the brightness of the coloring composition tends to be improved.
The number of carbon atoms in the aromatic heterocycle is not particularly limited, but is preferably 2 or more, more preferably 3 or more, preferably 15 or less, more preferably 10 or less, still more preferably 5 or less, and particularly preferably 4 or less. .. When it is at least the above lower limit value, the durability after firing tends to be improved, and when it is at least the above upper limit value, the brightness of the coloring composition tends to be improved.
The aromatic heterocycle may have a substituent, and the substituents which may have a substituent include a methyl group, an ethyl group, an n-propyl group, a 2-propyl group, an n-butyl group and an isobutyl. Examples thereof include a group, a tert-butyl group, a cyclohexyl group, a cyclohexylmethyl group, a cyclohexylethyl group, a 3-methylbutyl group and the like.

Among the aromatic heterocycles, the triarylmethane compound preferably has low basicity from the viewpoint of reactivity with sp2 carbon, and the pKa at the time of protonation in water is preferably 7 or less, preferably 6 or less. Is more preferable, 5 or less is further preferable, and usually 0.5 or more.

Specific examples of the aromatic heterocycle include pyrol, imidazole, pyrazole, triazole, oxazole, thiazole, indole, isoindole, benzoimidazole, purine, benzopyrazole, benzotriazole, benzoxazole, benzothiazole, carbazole, furan, benzofuran, Dibenzofuran, thiophene benzothiophene, dibenzothiophene, pyridine, pyrazine, pyradazine, pyrimidine, triazine, phenanthridine, quinoline, isoquinoline, quinazoline, quinoxalin, cinnoline, pteridine, aclysine, oxadiazol, pyrroylmidazole, pyrrolopyrazole, pyrrolopyrrole, Examples thereof include thienopyrrole, thienothiophene, flopyrol, flofuran, thienoflan, benzoisoxazole, benzoisothiazole, perimidine, porphyrin, etc. Among these, imidazole ring and pyridine from the viewpoint of durability after firing and cost in the synthetic process of dispersant. A ring or a carbazole ring is preferable, an imidazole ring or a pyridine ring is more preferable, and an imidazole ring is further preferable.

The chemical structure of the dispersant is not particularly limited, and examples thereof include those having an adsorbent group adsorbed on the colorant on the pigment or the like and a compatible chain compatible with the resin or the like for forming a steric hindrance. As described above, the adsorbent group in the dispersant (b1) contains an aromatic heterocycle. On the other hand, the compatible chain is not particularly limited as long as it is oriented toward a resin or the like, and examples thereof include an alkyl chain, a polyether chain, and a polyester chain.

The weight average molecular weight of the dispersant (b1) is not particularly limited, but is preferably 1000 or more, more preferably 2000 or more, further preferably 3000 or more, particularly preferably 4000 or more, preferably 1,000,000 or less, and more preferably 100,000 or less. , 50,000 or less is more preferable, and 20,000 or less is particularly preferable. The dispersion stability tends to be improved by setting the value to the lower limit value or more and to the upper limit value or less.

The acid value of the dispersant (b1) is not particularly limited, but is preferably 50 mgKOH / g or less, more preferably 20 mgKOH / g or less, further preferably 10 mgKOH / g or less, and particularly preferably 0 mgKOH / g. When the value is not more than the upper limit, the dispersion stability of the pigment tends to be improved.

The amine value of the dispersant (b1) is not particularly limited, but is preferably 1 mgKOH / g or more, more preferably 2 mgKOH / g or more, further preferably 5 mgKOH / g or more, particularly preferably 10 mgKOH / g or more, and 200 mgKOH / g. The following is preferable, 180 mgKOH / g or less is more preferable, 160 mgKOH / g or less is further preferable, and 140 mgKOH / g or less is particularly preferable. When it is at least the above lower limit value, the dispersion stability of the pigment tends to be improved, and when it is at least the above upper limit value, the durability after firing tends to be improved.

The types of dispersants include, for example, urethane-based dispersants, acrylic-based dispersants, polyethyleneimine-based dispersants, polyallylamine-based dispersants, dispersants composed of monomers having an amino group and macromonomers, and polyoxyethylene alkyl ethers. Examples thereof include system dispersants, polyoxyethylene diester dispersants, polyether phosphoric acid dispersants, polyester phosphoric acid dispersants, sorbitan aliphatic ester dispersants, aliphatic modified polyester dispersants, and the like. Among these, a urethane-based dispersant is preferable from the viewpoint of durability after firing, and an acrylic-based dispersant is preferable from the viewpoint of less influence on the optical characteristics of the obtained pattern due to less absorption of visible light.

Specific examples of such dispersants include EFKA (registered trademark, manufactured by BASF), DISPERBYK (registered trademark, manufactured by Big Chemie), Disparon (registered trademark, manufactured by Kusumoto Kasei Co., Ltd.), and SOLSPERSE under the trade names. (Registered trademark, manufactured by Lubrizol), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), Ajispar (registered trademark, manufactured by Ajinomoto Co., Ltd.), TEGO DISPER (registered trademark, manufactured by Ebony) And so on.
These dispersants may be used alone or in combination of two or more.

Examples of urethane-based and acrylic-based polymer dispersants include DISPERBYK161, 162, 163, and 167 series (all urethane-based), EFKA4046, 4047, 7494 series (all urethane-based), and EFKA4320 series (acrylic-based). ..

To specifically exemplify a preferable chemical structure as a urethane-based polymer dispersant, for example, it is the same as a polyisocyanate compound and a compound having one or two hydroxyl groups in the molecule and having a number average molecular weight of 300 to 10,000. Examples thereof include a dispersed resin having a weight average molecular weight of 1,000 to 200,000, which is obtained by reacting an active hydrogen with a compound having an aromatic heterocyclic group in the molecule.

Examples of the above polyisocyanate compounds include paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, trizine diisocyanate and the like. Aromatic diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, aliphatic diisocyanate such as dimerate diisocyanate, isophorone diisocyanate, 4,4'-methylenebis (cyclohexylisocyanate), ω, ω Alicyclic diisocyanate such as ′-diisosinate dimethylcyclohexane, aliphatic diisocyanate having aromatic ring such as xylylene diisocyanate, α, α, α ′, α ′-tetramethylxylylene diisocyanate, lysine ester triisocyanate, 1, 6,11-Undecantriisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, tris (isocyanatephenylmethane), tris (isocyanatephenyl) thiophosphate Such as triisocyanates, trimerics thereof, water adducts, and polyol adducts thereof. The polyisocyanate is preferably a trimer of organic diisocyanate, and most preferably a trimer of tolylene diisocyanate and a trimer of isophorone diisocyanate. One of these may be used alone, or two or more thereof may be used in combination.

As a method for producing an isocyanate trimer, the polyisocyanate is subjected to an isocyanate group moiety using an appropriate trimerization catalyst, for example, tertiary amines, phosphines, alkoxides, metal oxides, carboxylates and the like. A method of obtaining a desired isocyanurate group-containing polyisocyanate by performing a specific trimerization, stopping the trimerization by adding a catalytic poison, and then removing the unreacted polyisocyanate by solvent extraction and thin film distillation.

Compounds having one or two hydroxyl groups in the same molecule and having a number average molecular weight of 300 to 10,000 include polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol, and the like, and one terminal hydroxyl group of these compounds has the number of carbon atoms. Examples thereof include those alkoxylated with 1 to 25 alkyl groups and mixtures of two or more of these.
Examples of the polyether glycol include a polyether diol, a polyether ester diol, and a mixture of two or more of these. Examples of the polyether diol include those obtained by alkylene oxide alone or by copolymerizing, for example, polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol and them. A mixture of two or more of the above can be mentioned.

The polyether ester diol is obtained by reacting an ether group-containing diol or a mixture with another glycol with a dicarboxylic acid or an anhydride thereof, or by reacting a polyester glycol with an alkylene oxide, for example, poly (poly). Oxytetramethylene) adipate and the like can be mentioned. The most preferable polyether glycol is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, or a compound in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.

As polyester glycol, dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or their anhydrides and glycols (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, etc.) Dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol , 2-Methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1 , 6-Hexanediol, 2-methyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2 , 5-Hexanediol, 1,8-octamethylene glycol, 2-methyl-1,8-octamethylene glycol, aliphatic glycols such as 1,9-nonanediol, alicyclic glycols such as bishydroxymethylcyclohexane, xyl Aroglycol such as len glycol and bishydroxyethoxybenzene, N-alkyldialkanolamine such as N-methyldiethanolamine, etc.) obtained by polycondensation, for example, polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, Polylactone diols or polylactone monools obtained by using polyethylene / propylene adipate or the like, or the above diols or monovalent alcohols having 1 to 25 carbon atoms as an initiator, for example, polycaprolactone glycol, polymethylvalerolactone and 2 thereof. Glycols of seeds and above can be mentioned. The most preferable polyester glycol is polycaprolactone glycol or polycaprolactone using an alcohol having 1 to 25 carbon atoms as an initiator.

Polycarbonate glycol includes poly (1,6-hexylene) carbonate, poly (3-methyl-1,5-pentylene) carbonate and the like, and polyolefin glycol includes polybutadiene glycol, hydrogenated polybutadiene glycol, hydrogenated polyisoprene glycol and the like. Can be mentioned.
One of these may be used alone, or two or more thereof may be used in combination.

The number average molecular weight of a compound having one or two hydroxyl groups in the same molecule is usually 300 to 10,000, preferably 500 to 6,000, and more preferably 1,000 to 4,000.

A compound having an active hydrogen and an aromatic heterocyclic group in the same molecule used in the present invention will be described.
Examples of active hydrogen, that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom or a sulfur atom, include a hydrogen atom in a functional group such as a hydroxyl group, an amino group or a thiol group, and among them, an amino group, particularly a primary group. The hydrogen atom of the amino group of is preferable.

The aromatic heterocyclic group is not particularly limited, and examples thereof include a heterocyclic structure having an alkyl group having 1 to 4 carbon atoms, more specifically, an imidazole ring, a pyridine ring, a carbazole ring, and the like.

When the aromatic heterocyclic group has a nitrogen-containing heterocyclic structure, the nitrogen-containing heterocycle includes a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, an indol ring, a carbazole ring, an indazole ring, and a benzimidazole ring. Nitrogen-containing hetero 5-membered ring such as benzotriazole ring, benzoxazole ring, benzothiazole ring, benzothiazazole ring, pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acrydin ring, isoquinoline ring and the like. A member ring can be mentioned. Of these nitrogen-containing heterocycles, preferred are imidazole rings, pyridine rings, or carbazole rings.

One of these may be used alone, or two or more thereof may be used in combination.

The preferable blending ratio of the raw material for producing the urethane-based polymer dispersant is 10 compounds having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the same molecule with respect to 100 parts by mass of the polyisocyanate compound. ~ 200 parts by mass, preferably 20 to 190 parts by mass, more preferably 30 to 180 parts by mass, 0.2 to 25 parts by mass, preferably 0.3 parts by mass of the compound having an active hydrogen and a tertiary amino group in the same molecule. ~ 24 parts by mass.

The urethane-based polymer dispersant is produced according to a known method for producing a polyurethane resin. The solvent used for production is usually ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone and isophorone, esters such as ethyl acetate, butyl acetate and cellosolve acetate, benzene, toluene, xylene and hexane. Hydrocarbons such as, diacetone alcohol, isopropanol, second butanol, some alcohols such as tertiary butanol, chlorides such as methylene chloride and chloroform, ethers such as tetrahydrofuran and diethyl ether, dimethylformamide, N-methyl. An aprotonic polar solvent such as pyrrolidone or dimethylsulfoxide is used. One of these may be used alone, or two or more thereof may be used in combination.

In the above production, a urethanization reaction catalyst is usually used. Examples of this catalyst include tin-based catalysts such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate and stanas octoate, iron-based catalysts such as iron acetylacetonate and ferric chloride, triethylamine and triethylenediamine. Examples include grade amines. One of these may be used alone, or two or more thereof may be used in combination.

The amount of the compound having active hydrogen and a tertiary amino group in the same molecule is preferably controlled in the range of 1 to 100 mgKOH / g in terms of the amine value after the reaction. More preferably, it is in the range of 5 to 95 mgKOH / g. The amine value is a value expressed by the number of mg of KOH corresponding to the acid value by neutralizing and titrating the basic amino group with an acid. If the amine value is lower than the above range, the dispersibility tends to decrease, and if it exceeds the above range, the developability tends to decrease.

When the isocyanate group remains in the polymer dispersant by the above reaction, it is preferable to crush the isocyanate group with an alcohol or an amino compound because the stability of the product with time becomes higher.

On the other hand, as the acrylic polymer dispersant, a random copolymer of an unsaturated group-containing monomer having an aromatic heterocyclic group and an unsaturated group-containing monomer having no aromatic heterocyclic group. , Graft copolymers and block copolymers are preferably used. These copolymers can be produced by known methods.

Specific examples of the unsaturated group-containing monomer having an aromatic heterocyclic group include N-vinylimidazole, 4-vinylpyridine, N-vinylcarbazole, and N- (meth) acryloylimidazole. One of these may be used alone, or two or more thereof may be used in combination.

Examples of the unsaturated group-containing monomer having no aromatic heterocycle include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. Isobutyl (meth) acrylate, t-butyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxymethyl (meth) acrylate, 2-ethylhexyl ( Meta) acrylate, isobornyl (meth) acrylate, tricyclodecane (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, N-vinylpyrrolidone, styrene and its derivatives, α-methylstyrene, N-cyclohexylmaleimide, N-phenylmaleimide , N-substituted maleimides such as N-benzylmaleimide, acrylonitrile, vinyl acetate and polymethyl (meth) acrylate macromonomers, polystyrene macromonomers, poly2-hydroxyethyl (meth) acrylate macromonomers, polyethylene glycol macromonomers, polypropylene glycol macromonomers , Macromonomers such as polycaprolactone macromonomers and the like. One of these may be used alone, or two or more thereof may be used in combination.

The acrylic polymer dispersant is particularly preferably an AB or BAB block copolymer composed of an A block having an aromatic heterocycle and a B block having no aromatic heterocycle. In this case, in addition to the partial structure derived from the unsaturated group-containing monomer containing the aromatic heterocycle, the A block contains a partial structure derived from the unsaturated group-containing monomer not containing the aromatic heterocycle. It may be contained, and these may be contained in the A block in any aspect of random copolymerization or block copolymerization.

The B block is composed of a partial structure derived from an unsaturated group-containing monomer that does not contain the aromatic heterocycle, and one B block contains a partial structure derived from two or more kinds of monomers. These may be contained in the B block in any mode of random copolymerization or block copolymerization.
The AB or BAB block copolymer is prepared, for example, by the living polymerization method shown below.
The living polymerization method includes an anion living polymerization method, a cationic living polymerization method, and a radical living polymerization method. Among them, in the anion living polymerization method, the polymerization active species is an anion, and is represented by, for example, the following scheme.

In the above scheme, Ar ¹ is a monovalent organic group, Ar ² is a ^{monovalent organic group different from Ar 1} , M is a metal atom, and s and t are integers of 1 or more, respectively.

In the radical living polymerization method, the polymerization active species is a radical, and is shown by, for example, the following scheme.

In the above scheme, Ar ¹ is a monovalent organic group, Ar ² is a ^{monovalent organic group different from Ar 1} , j and k are each an integer of 1 or more, and ^Ra is a hydrogen atom or 1 It is a valent organic group, and R ^b is ^a hydrogen atom or a monovalent organic group different from Ra.

In synthesizing this acrylic polymer dispersant, JP-A-9-62002 and P.I. Lutz, P.M. Masson et al, Polym. Bull. 12, 79 (1984), B.I. C. Anderson, G.M. D. Andrews et al, Macromolecules, 14, 1601 (1981), K. et al. Hatada, K.K. Ute, et al, Polym. J. 17, 977 (1985), 18, 1037 (1986), Koichi Right Hand, Koichi Hatada, Polymer Processing, 36, 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Collection of Polymer Papers, 46, 189 (1989), M. Kuroki, T.K. Aida, J.M. Am. Chem. Sic, 109, 4737 (1987), Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43, 300 (1985), D.I. Y. Sogoh, W.M. R. A known method described in Hertler et al, Macromolecules, 20, 1473 (1987) and the like can be adopted.

The dispersant (b) in the coloring composition of the present invention contains a dispersant (b1), but may further contain another dispersant (b2).

The content ratio of the dispersant (b) in the coloring composition of the present invention is not particularly limited, but is preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 2% by mass or more in the total solid content. 4, 4% by mass or more is particularly preferable, 15% by mass or less is preferable, 10% by mass or less is more preferable, 8% by mass or less is further preferable, and 6% by mass or less is particularly preferable. When it is at least the lower limit value, the dispersion stability tends to be improved, and when it is at least the upper limit value, the brightness tends to be high.

The content ratio of the dispersant (b1) in the coloring composition of the present invention is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and 1% by mass or more in the total solid content. More preferably, 2% by mass or more is particularly preferable, 10% by mass or less is preferable, 7% by mass or less is more preferable, 5% by mass or less is further preferable, and 3% by mass or less is particularly preferable. By setting the value to the lower limit value or more, and by setting the value to the upper limit value or less, the durability after firing tends to be improved.

[(C) Solvent]
The coloring composition of the present invention contains (c) a solvent. (C) The solvent has a function of dissolving or dispersing each component contained in the coloring composition and adjusting the viscosity.
As the solvent (c), any solvent may be used as long as it can dissolve or disperse each component constituting the coloring composition, and a solvent having a boiling point in the range of 100 to 250 ° C. is preferably selected. It has a boiling point of 100 to 200 ° C., more preferably 120 to 170 ° C.

Examples of such a solvent include the following.
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol-monot-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, methoxymethylpentanol, propylene Glycol monoalkyl ethers such as glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, tripropylene glycol monomethyl ether;

Glycoldialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether;
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monoethyl Glycolalkyl ether acetates such as ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl acetate;

Ethers such as diethyl ether, dipropyl ether, diisopropyl ether, diamil ether, ethyl isobutyl ether, dihexyl ether;
Ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methylhexyl ketone, methylnonyl ketone;
Monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin;
Aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane;
Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;

Aromatic hydrocarbons such as benzene, toluene, xylene, cumene;
Amilformate, ethylformate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, cyclohexyl acetate, methylisobutyrate, ethylene glycol acetate, ethyl propionate, propylpropionate, butyl butyrate, isobutyl butyrate, isobutyric acid Methyl, ethyl caprilate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3- Chain or cyclic esters such as butyl methoxypropionate, γ-butyrolactone;
Alkoxycarboxylic acids such as 3-methoxypropionic acid, 3-ethoxypropionic acid;
Halogenated hydrocarbons such as butyl chloride, amilk chloride;
Ether ketones such as methoxymethylpentanone;
Nitriles such as acetonitrile and benzonitrile:
These solvents may be used alone or in combination of two or more.

It is preferable to contain glycol monoalkyl ethers in the solvent from the viewpoint of adhesion between the substrate and the coating film and the ability to form a uniform film thickness of the coating film. Of these, propylene glycol monomethyl ether is particularly preferable from the viewpoint of solubility of various constituents in the coloring composition.
Further, for example, when the above-mentioned other pigment is contained as an optional component, the coating property, surface tension, etc. are well-balanced, and the solubility of the component component in the coloring composition is relatively high. It is more preferable to use a mixture of ether acetates. In the coloring composition containing a pigment, glycol monoalkyl ethers have high polarity and tend to aggregate the pigment, which may reduce the storage stability such as increasing the viscosity of the coloring composition. Therefore, it is preferable that the content ratio of the glycol monoalkyl ethers is not excessively high, and (c) the content ratio of the glycol monoalkyl ethers in the solvent is preferably 5 to 50% by mass, more preferably 5 to 30% by mass. preferable.

Further, from the viewpoint of suitability for the slit coating method corresponding to recent large substrates and the like, it is also preferable to use a solvent having a boiling point of 150 ° C. or higher in combination. In this case, the content ratio of such a high boiling point solvent is preferably 0.5 to 50% by mass, more preferably 1 to 40% by mass, and particularly preferably 2 to 30% by mass with respect to the entire solvent (c). When it is at least the above lower limit value, for example, it tends to be easy to prevent dye components and the like from precipitating and solidifying at the tip of the slit nozzle to cause foreign matter defects. The slowdown tends to avoid problems such as poor tact in the vacuum drying process in the color filter manufacturing process and pre-baking pin marks.

The solvent having a boiling point of 150 ° C. or higher may be glycol alkyl ether acetates or glycol alkyl ethers. In this case, it is not necessary to separately contain a solvent having a boiling point of 150 ° C. or higher. ..
The coloring composition of the present invention may be used for producing a color filter by an inkjet method, but in the manufacturing of a color filter by an inkjet method, the ink emitted from the nozzle is very small, several to several tens of pL, and therefore the nozzle. Before landing around the mouth or in the pixel bank, the solvent tends to evaporate and the ink tends to concentrate and dry. In order to avoid this, it is preferable that the boiling point of the solvent is high, and specifically, it is preferable that the solvent (c) contains a solvent having a boiling point of 180 ° C. or higher. In particular, it is preferable to contain a solvent having a boiling point of 200 ° C. or higher, particularly preferably a boiling point of 220 ° C. or higher. The high boiling point solvent having a boiling point of 180 ° C. or higher is preferably 50% by mass or more in the solvent (c). When the proportion of such a high boiling point solvent is 50% by mass or more, the effect of preventing evaporation of the solvent from the ink droplets tends to be sufficiently exhibited.

The content ratio of the solvent (c) in the coloring composition of the present invention is not particularly limited, but is usually 99% by mass or less, preferably 90% by mass or less, more preferably 80% by mass or less, and is suitable for coating. Considering the viscosity and the like, it is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 70% by mass or more.

As described above, the coloring composition of the present invention contains (a) a coloring agent, (b) a dispersant, and (c) a solvent, and may further contain other components. For example, (d) a binder resin, (e) a photopolymerizable monomer, and (f) a photopolymerization initiator may be mentioned, and other components may be further contained if necessary.

[(D) Binder resin]
The coloring composition of the present invention may contain (d) a binder resin. (D) By containing the binder resin, there is a tendency that a cured film having a sufficient degree of curing can be formed. (D) Among the binder resins, an alkali-soluble resin is preferable from the viewpoint of forming a pattern by alkali development. For example, JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, JP-A-11-140144, JP-A-11-174224, JP-A-2000-56118, The polymer compounds described in each publication such as JP-A-2003-233179 can be used, and among them, the following resins (d-1) to (d-5) are preferable.

(D-1): With respect to a copolymer of an epoxy group-containing (meth) acrylate and another radically polymerizable monomer, unsaturated monobasic acid is added to at least a part of the epoxy groups of the copolymer. The resin to be added, or an alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl groups generated by the addition reaction (hereinafter, may be referred to as "resin (d-1)"). .)
(D-2): Carboxyl group-containing linear alkali-soluble resin (d-2) (hereinafter, may be referred to as "resin (d-2)").
(D-2'): A copolymer of a radically polymerizable monomer having a cyclic ether group having 2 to 4 carbon atoms and a radical polymerizable monomer having a carboxyl group, or a cyclic ether having 2 to 4 carbon atoms. A copolymer of a radical-polymerizable monomer having a group, a radical-polymerizable monomer having a carboxyl group, and another radical-polymerizable monomer different from these (d-3): the resin (d-2). Resin in which an epoxy group-containing unsaturated compound is added to the carboxyl radical portion of the above (hereinafter, may be referred to as "resin (d-3)").
(D-4): (Meta) acrylic resin (hereinafter, may be referred to as "resin (d-4)")
(D-5): Epoxy acrylate resin having a carboxyl group (hereinafter, may be referred to as "resin (d-5))."
Of these, resin (d-1) is particularly preferable, and the resin will be described below.

The resins (d-2) to (d-5) may be any resin as long as they are dissolved by an alkaline developer and have enough solubility to carry out the desired developing treatment. It is the same as that described as the same item in Japanese Patent Application Laid-Open No. 2009-025813. The same applies to the preferred embodiment.
As one of the particularly preferable resins of the resin (d-1), with respect to a copolymer of 5 to 90 mol% of epoxy group-containing (meth) acrylate and 10 to 95 mol% of another radically polymerizable monomer, A resin obtained by adding an unsaturated monobasic acid to 10 to 100 mol% of the epoxy groups of the copolymer, or a polybasic acid anhydride added to 10 to 100 mol% of the hydroxyl groups generated by the addition reaction. Examples thereof include the alkali-soluble resin obtained from the above.

Examples of the epoxy group-containing (meth) acrylate include glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. ) Acrylate glycidyl ether and the like can be exemplified. Of these, glycidyl (meth) acrylate is preferable. One of these epoxy group-containing (meth) acrylates may be used alone, or two or more thereof may be used in combination.

The other radically polymerizable monomer copolymerized with the epoxy group-containing (meth) acrylate is not particularly limited as long as the effect of the present invention is not impaired. For example, vinyl aromatics, dienes, (meth). Acrylic acid esters, (meth) acrylic acid amides, vinyl compounds, unsaturated dicarboxylic acid diesters, monomaleimides and the like can be mentioned, and in particular, mono (meth) having a structure represented by the following formula (III). Acrylic is preferred.

The repeating unit derived from the mono (meth) acrylate having the structure represented by the following formula (III) contains 5 to 90 mol% of the repeating units derived from "another radically polymerizable monomer". It is preferable that the content is 10 to 70 mol%, more preferably 15 to 50 mol%, and particularly preferably 15 to 50 mol%.

In the above formula (III), R ⁸⁹ represents a hydrogen atom or a methyl group, and R ⁹⁰ represents a structure represented by the following formula (IV).

In the above formula (IV), R ^{91 to} R ⁹⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ⁹⁶ and R ⁹⁸ may be connected to each other to form a ring.
The ^{ring formed by connecting R 96} and R ⁹⁸ is preferably an aliphatic ring, which may be saturated or unsaturated, and preferably has 5 to 6 carbon atoms.
Among them, as the structure represented by the formula (IV), the structure represented by the following structural formulas (IVa), (IVb), or (IVc) is particularly preferable.

As the mono (meth) acrylate having the structure represented by the formula (IV), one type may be used alone, or two or more types may be used in combination.
As the "other radically polymerizable monomer" other than the mono (meth) acrylate having the structure represented by the formula (IV), excellent heat resistance and strength of the coloring composition can be improved. Styrene, (meth) acrylate-n-butyl, (meth) acrylate-tert-butyl, (meth) acrylate cyclohexyl, (meth) acrylate isobolonyl, (meth) acrylate adamantyl, (meth) acrylate benzyl, Examples thereof include -2-hydroxyethyl (meth) acrylate, N-phenylmaleimide, and N-cyclohexylmaleimide.

The content of the repeating unit derived from at least one selected from the above-mentioned monomer group is preferably 1 to 70 mol%, more preferably 3 to 50 mol%.
A known solution polymerization method is applied to the copolymerization reaction between the epoxy group-containing (meth) acrylate and the other radically polymerizable monomer.
In the present invention, the copolymer of the epoxy group-containing (meth) acrylate and the other radically polymerizable monomer includes a repeating unit of 5 to 90 mol% derived from the epoxy group-containing (meth) acrylate, and the like. It is preferably composed of 10 to 95 mol% of the repeating unit derived from the radically polymerizable monomer of the above, more preferably 20 to 80 mol% of the former and 80 to 20 mol% of the latter, and 30 to 30 to 20 of the former. Those consisting of 70 mol% and the latter 70 to 30 mol% are particularly preferable.

When it is within the above range, the amount of the polymerizable component and the alkali-soluble component described later is sufficient, and the heat resistance and the strength of the film are sufficient, which is preferable.
An unsaturated monobasic acid (polymerizable component) is further reacted with a polybasic acid anhydride (alkali-soluble component) on the epoxy group portion of the epoxy group-containing copolymer synthesized as described above.
Here, as the unsaturated monobasic acid added to the epoxy group, known ones can be used, and examples thereof include unsaturated carboxylic acids having an ethylenically unsaturated double bond.

Specific examples include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, and the α-position is substituted with a haloalkyl group, an alkoxyl group, a halogen atom, a nitro group, a cyano group, or the like. Examples thereof include monocarboxylic acids such as (meth) acrylic acid. Of these, (meth) acrylic acid is preferable. One of these may be used alone, or two or more thereof may be used in combination.

By adding such a component, the binder resin used in the present invention can be imparted with polymerizable properties.
These unsaturated monobasic acids are usually added to 10 to 100 mol% of the epoxy groups of the copolymer, preferably 30 to 100 mol%, more preferably 50 to 100 mol%. When it is within the above range, it is preferable because the coloring composition is excellent in stability with time. As a method for adding an unsaturated monobasic acid to the epoxy group of the copolymer, a known method can be adopted.

Further, as the polybasic acid anhydride added to the hydroxyl group generated when the unsaturated monobasic acid is added to the epoxy group of the copolymer, known ones can be used.
For example, dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride; trimellitic anhydride, pyromellitic anhydride, benzophenone. Examples thereof include anhydrides of acids having three or more bases such as tetracarboxylic acid anhydride and biphenyltetracarboxylic acid anhydride. Of these, succinic anhydride and tetrahydrophthalic anhydride are preferable. One of these polybasic acid anhydrides may be used alone, or two or more thereof may be used in combination.

By adding such a component, alkali solubility can be imparted to the binder resin used in the present invention.
These polybasic acid anhydrides are usually added to 10 to 100 mol% of the hydroxyl groups generated by adding an unsaturated monobasic acid to the epoxy group of the copolymer, preferably 20 to 90 mol. %, More preferably 30-80 mol%.

When it is within the above range, the residual film ratio and solubility at the time of development are sufficient, which is preferable.
As a method for adding the polybasic acid anhydride to the hydroxyl group, a known method can be adopted.
Further, in order to improve the photosensitivity, after adding the above-mentioned polybasic acid anhydride, glycidyl (meth) acrylate or a glycidyl ether compound having a polymerizable unsaturated group is added to a part of the generated carboxyl groups. You may. The structure of such a resin is described in, for example, JP-A-8-297366 and JP-A-2001-89533.

(D) The polystyrene-equivalent weight average molecular weight (Mw) of the binder resin measured by GPC (gel permeation chromatography) is preferably 3000 or more, more preferably 5000 or more, preferably 100,000 or less, and preferably 50,000 or less. More preferably, it is more preferably 30,000 or less, and particularly preferably 10,000 or less. When it is within the above range, it is preferable in that heat resistance, film strength, and solubility in a developing solution are good.
As a guideline for the molecular weight distribution, the ratio of weight average molecular weight (Mw) / number average molecular weight (Mn) is preferably 2.0 to 5.0.

The acid value of the binder resin (d) is preferably 10 mg-KOH / g or more, more preferably 30 mg-KOH / g or more, further preferably 50 mg-KOH / g or more, and preferably 200 mg-KOH / g or less. 150 mg-KOH / g or less is more preferable, and 100 mg-KOH / g or less is further preferable. When it is at least the above lower limit value, the solubility in a developing solution tends to be good, and when it is at least the above upper limit value, film roughness tends to be suppressed.

The content ratio of the binder resin (d) in the coloring composition is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, and particularly preferably 30% by mass or more. Further, 80% by mass or less is preferable, 70% by mass or less is more preferable, 60% by mass or less is further preferable, 50% by mass or less is further preferable, and 40% by mass or less is particularly preferable. When it is equal to or more than the lower limit value, an appropriate film thickness tends to be secured for pattern formation by development, and when it is equal to or less than the upper limit value, the sensitivity tends to be appropriate for pattern formation by development.

[(E) Photopolymerizable Monomer]
The coloring composition of the present invention preferably contains (e) a photopolymerizable monomer. The photopolymerizable monomer is not particularly limited as long as it is a photopolymerizable low molecular weight compound, but is an addition-polymerizable compound having at least one ethylenic double bond (hereinafter referred to as “ethyleney compound”). In some cases).
The ethylenic compound is a compound having an ethylenic double bond such that when the coloring composition of the present invention is irradiated with active light, it is addition-polymerized and cured by the action of a photopolymerization initiator described later. The (e) photopolymerizable monomer in the present invention means a concept opposite to a so-called polymer substance, and includes dimers, trimers, and oligomers in addition to monomers in a narrow sense.

In the present invention, it is particularly desirable to use a polyfunctional ethylenic monomer having two or more ethylenically unsaturated bonds in one molecule. The number of ethylenically unsaturated bonds contained in the polyfunctional ethylenic monomer is not particularly limited, but is preferably 2 or more, more preferably 3 or more, still more preferably 5 or more, and preferably 15 or less, more preferably 10. It is as follows. When it is set to the lower limit value or more, the polymerizable property tends to be improved and the sensitivity tends to be high, and when it is set to the upper limit value or less, the developability tends to be improved.

(E) Examples of the ethylen compound in the photopolymerizable monomer include unsaturated carboxylic acids such as (meth) acrylic acid; esters of monohydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds and unsaturated carboxylic acids. Esther with; ester of aromatic polyhydroxy compound and unsaturated carboxylic acid; ester of unsaturated carboxylic acid and polyvalent carboxylic acid and polyvalent hydroxy compound such as the above-mentioned aliphatic polyhydroxy compound and aromatic polyhydroxy compound. Examples thereof include an ester obtained by a chemical reaction; an ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound with a (meth) acryloyl group-containing hydroxy compound; and the like.

Examples of the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethyl propantri (meth) acrylate, and trimethylol ethanetri (meth) acrylate. , Pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) Examples thereof include (meth) acrylic acid esters such as acrylate and glycerol (meth) acrylate. Further, an itaconic acid ester in which the (meth) acrylic acid portion of these (meth) acrylic acid esters is replaced with an itaconic acid moiety, a crotonic acid ester in which the crotonic acid moiety is replaced, a maleic acid ester in which the maleic acid moiety is replaced, or the like. Can be mentioned.

Examples of the ester of the aromatic polyhydroxy compound and the unsaturated carboxylic acid include hydroquinone di (meth) acrylate, resorcindi (meth) acrylate, and pyrogalloltri (meth) acrylate.
The ester obtained by the esterification reaction of the unsaturated carboxylic acid with the polyvalent carboxylic acid and the polyvalent hydroxy compound may be a single substance or a mixture. Typical examples are condensates of (meth) acrylic acid, phthalic acid, and ethylene glycol; condensates of (meth) acrylic acid, maleic acid, and diethylene glycol; condensation of (meth) acrylic acid, terephthalic acid, and pentaerythritol. Things; (meth) acrylic acid, adipic acid, butanediol, condensate of glycerin and the like can be mentioned.

Examples of the ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound with a (meth) acryloyl group-containing hydroxy compound include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; and alicyclics such as cyclohexane diisocyanate and isophorone diisocyanate. Formula diisocyanate; aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate, and (meth) acryloyl such as 2-hydroxyethyl (meth) acrylate and 3-hydroxy [1,1,1-tri (meth) acryloyloxymethyl] propane. Examples thereof include a reaction product with a group-containing hydroxy compound.

Other examples of the ethylenic compound used in the present invention include (meth) acrylamides such as ethylenebis (meth) acrylamide; allyl esters such as diallyl phthalate; and vinyl group-containing compounds such as divinylphthalate. ..
Among these, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferable, a (meth) acrylic acid ester of pentaerythritol or dipentaerythritol is more preferable, and dipentaerythritol hexa (meth) acrylate is particularly preferable.

Further, as the ethylenic compound, a monomer having an acid value can also be preferably used. Examples of the monomer having an acid value are esters of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an acid is obtained by reacting an unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride. A polyfunctional monomer having a group is preferable, and particularly preferably, the aliphatic polyhydroxy compound is at least one of pentaerythritol and dipentaerythritol in this ester.

One of these monomers may be used alone, but a mixture of two or more may be used because it is difficult to obtain a single compound in production.
Further, if necessary, (e) a polyfunctional monomer having no acid group and a polyfunctional monomer having an acid group may be used in combination as the photopolymerizable monomer.
The acid value of the polyfunctional monomer having an acid group is preferably 0.1 to 100 mg-KOH / g, and particularly preferably 5 to 80 mg-KOH / g.

Within the above range, the developing and dissolving characteristics are less likely to deteriorate, and manufacturing and handling are easy. Further, it is preferable because the photopolymerization performance does not easily deteriorate and the curability such as the surface smoothness of the pixel is good.
In the present invention, the polyfunctional monomer having a more preferable acid group is, for example, a mixture containing, for example, a succinic acid ester of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentaacrylate as a main component. This polyfunctional monomer can be used in combination with other polyfunctional monomers.

In the coloring composition of the present invention, the content ratio of these (e) photopolymerizable monomers is usually 10% by mass or more, preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 30% by mass or more, based on the total solid content. Is 35% by mass or more, and is usually 90% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less, still more preferably 60% by mass or less, and particularly preferably 50% by mass or less.
The ratio of (e) the photopolymerizable monomer to 100 parts by mass of the above-mentioned (a) colorant is usually 1 part by mass or more, preferably 10 parts by mass or more, more preferably 50 parts by mass or more, still more preferably 100 parts by mass. More than parts, more preferably 150 parts by mass or more, particularly preferably 200 parts by mass or more, and usually 300 parts by mass or less, preferably 200 parts by mass or less, more preferably 150 parts by mass or less.
If it is within the above range, photocuring is appropriate, adhesion failure during development is difficult to place, the cross section after development is difficult to form an inverted taper shape, and peeling phenomenon / removal failure due to reduced solubility is difficult to place. preferable.

[(F) Photopolymerization Initiator]
The coloring composition of the present invention preferably contains (f) a photopolymerization initiator for the purpose of curing the coating film. However, the curing method may be other than those using these initiators.
In particular, when the coloring composition of the present invention contains a resin having an ethylenic double bond as the component (d) or contains an ethylenic compound as the component (e), it directly absorbs light or emits light. It is preferable to use a photopolymerization initiator having a function of sensitizing and causing a decomposition reaction or a hydrogen abstraction reaction to generate a polymerization active radical. (F) When a photopolymerization initiator is contained, an additive such as a polymerization accelerator or a sensitizing dye may be used in combination.

The (f) photopolymerization initiator in the present invention is a component having a function of directly absorbing light and generating a polymerization active radical.

(F) Examples of the photopolymerization initiator include titanosen derivatives described in JP-A-59-152396, JP-A-61-151197, etc .; JP-A-10-300922, JP-A-11-174224. Hexaaryl imidazole derivatives described in JP-A, JP-A-2000-56118, etc .; Halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives, N. -Radical activators such as N-aryl-α-amino acids such as phenylglycine, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives; Examples thereof include oxime ester-based derivatives described in Japanese Patent Publication No. 80068.

Specific examples thereof include the photopolymerization initiator described in Pamphlet No. 2009/107734 of International Publication No. 2009 and the like.
Among these photopolymerization initiators, α-aminoalkylphenone derivatives, oxime ester derivatives, biimidazole derivatives, acetophenone derivatives, and thioxanthone derivatives are more preferable.
Examples of oxime ester derivatives include 2- (benzoyloxyimino) -1- [4- (phenylthio) phenyl] -1-octanone and O-acetyl-1- [6- (2-methylbenzoyl) -9. -Ethyl-9H-carbazole-3-yl] Ethanone oxime and compounds represented by the following formula (V) can be mentioned.

In formula (V), R ¹⁰¹ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, or a heteroaryl group having 4 to 25 carbon atoms. It represents an alkyl group, all of which may have a substituent, or R ¹⁰¹ may be attached to X or Z to form a ring.
R ¹⁰² is an alkanoyl group having 2 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 4 to 8 carbon atoms, an aryloyl group having 7 to 20 carbon atoms, and an alkoxycarbonyl group having 2 to 10 carbon atoms. , An aryloxycarbonyl group having 7 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, a heteroallyloyl group having 3 to 20 carbon atoms or an alkylaminocarbonyl group having 2 to 20 carbon atoms, all of which are shown. It may have a substituent.

X represents at least one of a divalent aromatic hydrocarbon ring group and an aromatic complex group formed by condensing two or more rings which may have a substituent.
Z represents an aromatic ring group which may have a substituent. )
Among the compounds represented by the formula (V), a compound in which X is a carbazole ring which may have a substituent and a fluorene ring which may have a substituent is preferable, and specifically. Examples thereof include compounds represented by the following formula (VI), and among them, compounds represented by the following formula (VII) are particularly preferable.

In formula (VI), R ¹⁰¹ , R ¹⁰² and Z are synonymous with the definitions in formula (V). R ^{103 to} R ¹⁰⁹ each independently represent a hydrogen atom or an arbitrary substituent.

In the formula (VII), R ^101a represents an alkyl group having 1 to 3 carbon atoms or a group represented by the following formula (VIIa).

In formula (VIIa), R ¹¹⁰ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, or a heteroarylalkyl group having 4 to 25 carbon atoms. Indicates a group. * Represents the binding site. )
R ^102a represents an alkanoyl group having 2 to 4 carbon atoms, and X represents a 3,6-carbazolyl group in which the nitrogen atom may be substituted with an alkyl group of 1 to 4 carbon atoms. Z represents a naphthyl group which may be substituted with a phenyl group or a morpholino group which may be substituted with an alkyl group.

A commercially available product may be used as the oxime-based initiator. Examples of commercially available products include OXE-01, OXE-02, OXE-03, OXE-04 (manufactured by BASF), TRONLYTR-PBG-304, TRONLYTR-PBG-309, TRONLYTR-PBG-305, TRONLYTR-PBG- 314, -3057, -326, -345, -346, -358, -363, -365 (manufactured by Changshu Powerful Electronics New Materials Co., Ltd. (CANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD)), N-1919, NCI -930, NCI-831 (manufactured by ADEKA Corporation) and the like can be mentioned.

Other photopolymerization initiators include benzoin alkyl ethers, anthraquinone derivatives; acetophenone derivatives such as 2-methyl- (4'-methylthiophenyl) -2-morpholino-1-propanone, 2-ethylthioxanthone, and 2 , 4-Dixanthone derivatives such as diethylthioxanthone, benzoic acid ester derivatives, aclysine derivatives, phenazine derivatives, anthraquin derivatives and the like. Commercially available products may be used as these initiators.

As commercially available products, for example, IRGACURE 651, IRGACURE 184, DAROCURE 1173, IRGACURE 2959, IRGACURE 127, IRGACURE 907, IRGACURE 369, IRGACURE 379EG, LUCIRIN TPO, IRGACURE 8 Is a registered trademark) and the like.

Among these photopolymerization initiators, α-aminoalkylphenone derivatives, thioxanthone derivatives, and oxime ester derivatives are more preferable. In particular, oxime ester derivatives are preferable.
Examples of the polymerization accelerator used as needed include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester; mercapto compounds having a heterocycle; aliphatic polyfunctional mercapto. Examples thereof include mercapto compounds such as compounds.
Examples of the mercapto compound having one -SH in the molecule include 2-mercaptooxazole, 2-mercaptothiazole, 2-mercaptobenzoimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, and 2-mercaptonicotinic acid. 2-Mercaptopyridine, 2-mercaptopyridine-3-ol, 2-mercaptopyridine-N-oxide, 4-amino-6-hydroxy-2-mercaptopyrimidine, 4-amino-6-hydroxy-2-mercaptopyrimidine, 4 -Amino-2-mercaptopyrimidine, 6-amino-5-nitroso-2-mercaptopyrimidine-4-ol, 4,5-diamino-6-hydroxy-2-mercaptopyrimidine, 4,6-diamino-2-mercaptopyrimidine , 2,4-Diamino-6-mercaptopyrimidine, 4,6-dihydroxy-2-mercaptopyrimidine, 4,6-dimethyl-2-mercaptopyrimidine, 4-hydroxy-2-mercapto6-methylpyrimidine, 4-hydroxy- 2-Mercapto-6-propylpyrimidine, 2-mercapto-4-methylpyrimidine, 2-mercaptopyrimidine, 3,4,5,6-tetrahydropyrimidine-2-thiol, 4,5-diphenylimidazol-2-thiol, 2 -Mercaptoimidazole, 2-mercapto 1-methylimidazole, 4-amino-3-hydrazino-5-mercapto 1,2,4-triazole, 3-amino-5-mercapto 1,2,4-triazole, 2-methyl- 4H-1,2,4-triazole-3-thiol, 4-methyl-4H-1,2,4-triazole-3-thiol, 2-amino-5-mercapto-1,3,4-thiazazole, 5- Amino-1,3,4-thiasazole-2-thiol, (furan-2-yl) methanethiol, 2-mercapto-5-thiazolidone, 2-mercaptothiazolin, 2-mercapto 4 (3H) -quinazolinone, 1-phenyl -1H-tetrazole-5-thiol, 2-quinoline thiol, 2-mercapto 5-methylbenzoimidazole, 2-mercapto 5-nitrobenzoimidazole, 6-amino-2-mercaptobenzothiazole, 5-chloro-2-mercaptobenzo Thiol, 6-ethoxy-2-mercaptobenzothiazole, 6-nitro-2-mercaptobenzothiazole, 2-mercaptonaphthoimidazole, 2-mercaptonaphthol Oxazole, 3-mercapto1,2,4-triazole, 4-amino-6-mercaptopyrazolo [2,4-d] pyridine, 2-amino-6-purinethiol, 6-mercaptopurine, 4-mercapto1H- Pyrazolo [2,4-d] pyrimidine and the like can be mentioned.
Examples of the mercapto compound having two -SH in the molecule include 1,2-dimercaptoethane, 1,3-dimercaptopropane, 1,4-dimercaptobutane, 2,3-dimercaptobutane, and 1,5-. Dimercaptopentane, 1,6-dimercaptohexane, 1,8-dimercaptooctane, 1,9-dimercaptononan, 1,10-dimercaptodecane, 2,3-dimercapto-1-propanol, dimercaptoerythritol, 1,2-Dimercaptobenzene, 1,2-benzenedimethanethiol, 1,4-benzenedimethanethiol, 1,3-benzenedithiol, 3,4-dimercaptotoluene, 4-chloro-1,3-di Mercaptobenzene, 2-hexylamino-4,6-dimercapto-1,3,5-triazine, 2-diethylamino-4,6-dimercapto-1,3,5-triazine, 2-cyclohexylamino-4,6-dimercapto -1,3,5-triazine, ethylene glycol bis (3-mercaptopropionate), 2,5-dimercapto-1,3,4-thiasiazol, 2,2-bis (2-hydroxy-3-mercaptopropoxyphenyl) Propane), butanediol bis (3-mercaptopropionate), butanediolbis (2-mercaptoacetate), butanediolbis (3-mercaptopropionate), ethylene glycol bis (2-mercaptoacetate), 1,4 -Bis (3-sulfanylbutyloxy) butane, 2,5-dimercapto-1,3,4-thiadiazol and the like can be mentioned.
Examples of the mercapto compound having three -SH in the molecule include trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), and trimethylolpropane tris (3-mercaptoacetate), 1. , 2,6-Hexanetriol trimethylolglycolate and the like.
Examples of the mercapto compound having four -SH in the molecule include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), trishydroxyethyltris (3-mercaptopropionate), and penta. Examples thereof include erythritol tetrakis (4-mercaptobutyrate).

As these photopolymerization initiators and polymerization accelerators, one type may be used alone, or two or more types may be used in combination.
In addition, a sensitizing dye is used for the purpose of increasing the sensitivity, if necessary. As the sensitizing dye, an appropriate one is used depending on the wavelength of the image exposure light source. For example, the xanthene dyes described in JP-A-4-221958, JP-A-4-219756, etc .; A cumarin dye having a heterocycle described in JP-A-239703, JP-A-5-289335, etc .; 3-Ketokumarin dye described in JP-A-3-239703, JP-A-5-289335, etc .; Pyrromethene dyes described in JP-A-6-19240 and the like; JP-A-47-2528, JP-A-54-155292, JP-A-45-373777, JP-A-48-84183, JP-A-48-84183, JP-A. Japanese Patent Application Laid-Open No. 52-112681, Japanese Patent Application Laid-Open No. 58-15503, Japanese Patent Application Laid-Open No. 60-88805, Japanese Patent Application Laid-Open No. 59-56403, Japanese Patent Application Laid-Open No. 2-69, Japanese Patent Application Laid-Open No. 57-168808 , JP-A-5-107761, JP-A-5-210240, JP-A-4-288818, and the like, and examples thereof include dyes having a dialkylaminobenzene skeleton.
The sensitizing dye may also be used alone or in combination of two or more.

In the coloring composition of the present invention, the content ratio of these (f) photopolymerization initiators is usually 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1% by mass, based on the total solid content. The above is more preferably 3% by mass or more, still more preferably 5% by mass or more, particularly preferably 7% by mass or more, and usually 40% by mass or less, preferably 30% by mass or less, more preferably 20% by mass. Below, it is more preferably 15% by mass or less, and particularly preferably 12% by mass or less. When it is set to the lower limit value or more, the decrease in sensitivity to the exposed light tends to be suppressed, and when it is set to the upper limit value or less, the decrease in solubility of the unexposed portion in the developing solution and the accompanying development failure can be suppressed. There is.

[Other optional ingredients]
In addition to the above-mentioned components, the coloring composition of the present invention includes a surfactant, a thermosetting compound, a thermal polymerization initiator, a plasticizer, a thermal polymerization inhibitor, a storage stabilizer, a surface protectant, an adhesion improver, and a development agent. It may contain an improver or the like. As these optional components, for example, various compounds described in JP-A-2007-113000 can be used. When a pigment is contained, a dispersion aid may be contained.

[Method for preparing coloring composition]
In the present invention, the coloring composition can be prepared by an appropriate method, for example, (a) a coloring agent and (b) a dispersant are mixed together with (c) a solvent and an optional component used as necessary. Can be prepared by

Further, a colorant-containing liquid containing (a) a colorant, (b) a dispersant, and (c) a solvent may be prepared, and an arbitrary component such as (d) a binder resin may be mixed therewith.
In addition, as a preparation method when (a) a pigment is contained as a colorant, (a) in a solvent containing a colorant, (b) in the presence of a dispersant and a dispersion aid to be added as needed, depending on the case. (D) A colorant dispersion liquid is prepared by mixing and dispersing while pulverizing using, for example, a paint shaker, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like together with a part of the binder resin. Examples thereof include a method of preparing by adding (d) a binder resin,, if necessary, (e) a photopolymerizable monomer, (f) a photopolymerization initiator, and the like to the colorant dispersion liquid and mixing them. ..

[Application of coloring composition]
The coloring composition of the present invention is usually in a state in which all the constituent components are dissolved or dispersed in a solvent. A cured product can be obtained by supplying such a coloring composition onto a substrate and curing it. As described above, the cured product of the present invention is composed of the coloring composition of the present invention, and this cured product is used as a constituent member constituting an image display device such as a liquid crystal display device or an organic EL display device such as a color filter. Can be done.
Hereinafter, as an application example of the coloring composition of the present invention, an application of a color filter as a pixel and an image display device using them will be described. Specific examples of the image display device include a liquid crystal display device (panel) and an organic EL display device.

<Color filter>
The color filter of the present invention has pixels formed by using the coloring composition of the present invention.
The method for forming the color filter of the present invention will be described below.
The pixels of the color filter can be formed by various methods. Here, a case of forming by a photolithography method using a photopolymerizable coloring composition will be described as an example, but the production method is not limited to this.

First, a black matrix is formed on the surface of the substrate so as to partition the portion forming the pixel, if necessary, and the coloring composition of the present invention is applied onto the substrate, and then prebaked to obtain a solvent. Is evaporated to form a coating film. Next, the coating film is exposed to a photomask, then developed with an alkaline developer to dissolve and remove the unexposed portion of the coating film, and then post-baked to obtain red, green, and blue colors. A color filter can be produced by forming a pixel pattern.

In the present invention, it is particularly preferable that the pixels formed by using the coloring composition of the present invention are blue pixels.
The substrate used for forming the pixels is not particularly limited as long as it is transparent and has an appropriate strength, but for example, a polyester resin, a polyolefin resin, a polycarbonate resin, an acrylic resin, or a thermoplastic resin. Examples include sheet-made sheets, epoxy resins, thermoplastic resins, and various types of glass.

Further, if desired, these substrates may be subjected to appropriate pretreatment such as a thin film forming treatment with a silane coupling agent or a urethane resin, a surface treatment such as a corona discharge treatment or an ozone treatment.
When the coloring composition is applied to the substrate, examples thereof include a spinner method, a wire bar method, a flow coating method, a slit and spin method, a die coating method, a roll coating method, and a spray coating method. Of these, the slit-and-spin method and the die coat method are preferable.

The thickness of the coating film after drying is usually 0.2 to 20 μm, preferably 0.5 to 10 μm, and particularly preferably 0.8 to 5.0 μm.
When it is within the above range, it is preferable in that the gap adjustment in the pattern development and the liquid crystal cell formation step is easy and the desired color development is easy.
As the radiation used at the time of exposure, for example, visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays and the like can be used, but radiation having a wavelength in the range of 190 to 450 nm is preferable.

The light source for using radiation having a wavelength of 190 to 450 nm used for image exposure is not particularly limited, but for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, and the like. Lamp light sources such as medium-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, and fluorescent lamps; laser light sources such as argon ion lasers, YAG lasers, excima lasers, nitrogen lasers, helium cadmium lasers, and semiconductor lasers can be mentioned. An optical filter can also be used when irradiating light of a specific wavelength for use.

The exposure amount of radiation is preferably 10 to 10,000 J / m ^2.
Examples of the alkali developing solution include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium silicate, potassium silicate, sodium metasilicate, and sodium phosphate. Inorganic alkaline compounds such as potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide; mono-ethanolamine, di-ethanolamine, tri-ethanolamine, mono-methylamine, Di-methylamine, tri-methylamine, mono-ethylamine, di-ethylamine, tri-ethylamine, mono-isopropylamine, di-isopropylamine, n-butylamine, mono-isopropanolamine, di-isopropanolamine, tri-isopropanolamine , Ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), an aqueous solution of an organic alkaline compound such as choline is preferable.

An appropriate amount of a water-soluble organic solvent such as isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol, or a surfactant can be added to the alkaline developer. After alkaline development, it is usually washed with water.
As the developing method, any method such as a dipping developing method, a spray developing method, a brush developing method, and an ultrasonic developing method can be used. The developing conditions are preferably 5 to 300 seconds at room temperature (23 ° C.).

The conditions of the development process are not particularly limited, but the development temperature is usually in the range of 10 ° C. or higher, particularly 15 ° C. or higher, further 20 ° C. or higher, and usually 50 ° C. or lower, particularly 45 ° C. or lower, further 40 ° C. or lower. Is preferable. The developing method can be any one of a dipping developing method, a spray developing method, a brush developing method, an ultrasonic developing method and the like.

When the color filter produced in this way is used in a liquid crystal display device, a transparent electrode such as ITO is formed on the image as it is, and used as a part of parts such as a color display and a liquid crystal display device. Although it is used, in order to improve surface smoothness and durability, a top coat layer such as polyamide or polyimide can be provided on the image if necessary. Further, in some applications such as a plane orientation type drive system (IPS mode), a transparent electrode may not be formed. Further, in the vertically oriented drive system (MVA mode), ribs may be formed. Further, instead of the bead spraying type spacer, a pillar structure (photospacer) by a photolithography method may be formed.

<Image display device>
The image display device of the present invention has the cured product of the present invention, and examples thereof include those having a color filter. Examples of the image display device include a liquid crystal display device and an organic EL display device.

<Liquid crystal display>
The liquid crystal display device of the present invention uses the above-mentioned color filter of the present invention. The model and structure of the liquid crystal display device of the present invention are not particularly limited, and the liquid crystal display device of the present invention can be assembled according to a conventional method using the color filter of the present invention.
For example, the liquid crystal display device of the present invention can be formed by the method described in "Liquid Crystal Display Handbook" (Nikkan Kogyo Shimbun, published on September 29, 1989, by the 142nd Committee of the Japan Society for the Promotion of Science).

<Organic EL display device>
When producing an organic EL display device having the color filter of the present invention, for example, as shown in FIG. 1, the organic EL display device is organic on a blue color filter in which pixels 20 are formed by the coloring composition of the present invention on a transparent support substrate 10. A multicolored organic EL element is produced by laminating the organic illuminant 500 via the protective layer 30 and the inorganic oxide film 40.

As a method of laminating the organic illuminant 500, a method of sequentially forming a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light emitting layer 53, an electron injection layer 54, and a cathode 55 on the upper surface of the color filter, or Examples thereof include a method of bonding the organic light emitter 500 formed on another substrate onto the inorganic oxide film 40. The organic EL element 100 produced in this manner can be applied to both a passive drive type organic EL display device and an active drive type organic EL display device.

Next, the present invention will be described in more detail with reference to synthetic examples, examples and comparative examples, but the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded.
(Synthesis Example 1: Synthesis of Triarylmethane Compound A)

Under a nitrogen atmosphere, N, N-dimethylformamide (DMF) (60 mL) was added to N-ethyl-o-toluidine (21.6 g, 160 mmol), and the mixture was cooled to 5 ° C. or lower. Potassium t-butoxide (18.0 g, 160 mmol) was added in several portions while maintaining 5 ° C. or lower. Next, a solution of 4,4-difluorobenzophenone (8.73 g, 40.0 mmol) in N, N-dimethylformamide (DMF) (35 mL) was added dropwise over 30 minutes, taking care to keep the temperature below 15 ° C. After completion of the dropping, the temperature was raised to room temperature, and the mixture was further heated and stirred at 50 ° C. for 3 hours. After completion of the reaction, the mixture was allowed to cool to room temperature and poured into water (100 mL). This was extracted twice with toluene (50 mL), washed 3 times with water (20 mL), and then the solvent was distilled off with an evaporator. The obtained solid was purified by silica gel column chromatography (hexane / ethyl acetate = 100/0 to 66/34 (volume ratio)) to obtain Compound 1 (3.08 g, yield 17%).

Under a nitrogen atmosphere, 1-iodonaphthalene (5.1 g, 20 mmol), 2-methylcyclohexylamine (4.7 g, 41 mmol), sodium t-butoxide (2.4 g, 25 mmol), tris (dibenzylideneacetone) (chloroform). 2. A mixture of dipalladium (0) (52 mg, 0.050 mmol), 2,2'-(diphenylphosphino) -1,1'-binaphthyl (96 mg, 0.15 mmol) and toluene (50 mL) at 100 ° C. It was stirred for 5 hours. After cooling to room temperature, the mixture was filtered off, and the filtrate was washed with saturated aqueous ammonium chloride solution and saturated aqueous sodium chloride solution, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. Purification by silica gel column chromatography (hexane / ethyl acetate = 100/0 to 95/5 (volume ratio)) gave compound 2 (3.6 g, yield 75%).

Under a nitrogen atmosphere, the mixture of compound 1 (610 mg, 1.36 mmol), compound 2 (336 mg, 1.40 mmol) and toluene (10 mL) was stirred at room temperature until dissolved. Phosphoryl oxychloride (312 mg, 2.04 mmol) was added dropwise over 5 minutes, and after the addition, the mixture was heated to 80 to 85 ° C., and the mixture was heated and stirred as it was for 9 hours. Further, phosphorus oxychloride (208 mmol, 1.36 mmol) was added dropwise, and the mixture was heated and stirred as it was for 4 hours, and then allowed to cool to room temperature. Water (10 mL) was added and the mixture was stirred at room temperature for 1 hour. Chloroform (10 mL) was added to extract the organic layer, washed 3 times with water (10 mL), and then the solvent was evaporated with an evaporator. The obtained solid was dissolved in chloroform (10 mL), purified by silica chromatography (developing solvent: chloroform / methanol = 100/0 to 82/8 (volume ratio)), and the blue solid compound 3 (590 mg, yield). 61%) was obtained.

Under a nitrogen atmosphere, a mixed solution of Compound 3 (0.59 g, 0.84 mmol), methanol (5 mL) and bis (trifluoromethanesulfonyl) imidelithium (0.24 g, 0.84 mmol) was added at an outside temperature of 50 ° C. The mixture was heated and stirred for 5 hours. After allowing to cool to room temperature and distilling off the solvent with an evaporator, the mixture was washed with a mixed solution of methanol / water = 2/1 (volume ratio) (30 mL). The obtained solid is dissolved in chloroform (10 mL) and purified by silica chromatography (developing solvent: chloroform / methanol = 94/6 to 87/13 (volume ratio)) to obtain a blue solid triarylmethane-based compound A ( 0.50 g, yield 62%) was obtained.

Triarylmethane compound A was dissolved in propylene glycol monomethyl ether acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 35/65 (volume ratio) by 10 mass ppm. At this time, the maximum absorption wavelength (λmax) was 575 nm, and the gram absorption coefficient (g) was 81.8 Lg ^-1 cm ^-1 . The results of liquid chromatograph-mass spectrometry of this compound are shown below. The mass at this time indicates the mass of the triarylmethane cation site.
LCMS (ESI, posi) m / z 670 (M ⁺ C ₄₈ H ₅₂ N ₃ )

(Synthesis Example 2: Synthesis of Resin A)
145 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) was stirred while substituting with nitrogen, and the temperature was raised to 120 ° C. Here, 5.2 parts by mass of styrene, 132 parts by mass of glycidyl methacrylate, 4.4 parts by mass of monomethacrylate FA-513M (manufactured by Hitachi Kasei Co., Ltd.) having a tricyclodecane skeleton and 2.2'-azobis-2-methylbutyro. A mixed solution of 8.47 parts by mass of nitrile was added dropwise over 3 hours, and stirring was continued at 90 ° C. for 2 hours. Next, the inside of the reaction vessel was replaced with air, 1.1 parts by mass of trisdimethylaminomethylphenol and 0.19 parts by mass of hydroquinone were added to 67.0 parts by mass of acrylic acid, and the reaction was continued at 100 ° C. for 12 hours. Then, 15.2 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.2 parts by mass of triethylamine were added, and the mixture was reacted at 100 ° C. for 3.5 hours. The polystyrene-equivalent weight average molecular weight Mw of the resin solution thus obtained measured by GPC was about 9000 and the acid value was 25 mgKOH / g. Propylene glycol monomethyl ether acetate was added to this resin solution so that the solid content was 40% by mass, and the resin A was used.

(Synthesis Example 3: Synthesis of Resin B)
"NC3000H" (epoxy equivalent 288, softening point 69 ° C., manufactured by Nippon Kayaku Co., Ltd.) 400 parts by mass, 102 parts by mass of acrylic acid, 0.3 parts by mass of p-methoxyphenol, 5 parts by mass of triphenylphosphine, and propylene glycol monomethyl 264 parts by mass of ether acetate (PGMEA) was charged into a reaction vessel, and the mixture was stirred at 95 ° C. until the acid value became 3 mgKOH / g or less. It took 9 hours for the acid value to reach the target (2.2 mgKOH / g). Next, 151 parts by mass of tetrahydrophthalic anhydride was further added and reacted at 95 ° C. for 4 hours to obtain a resin solution having an acid value of 102 mgKOH / g and a polystyrene-equivalent weight average molecular weight Mw measured by GPC of 3900. Propylene glycol monomethyl ether acetate was added to this resin solution so that the solid content was 44% by mass, and the resin B was used.

(Synthesis Example 4: Synthesis of Initiator)
3- (2-acetoxyimino-1,5-dioxo-5-methoxypentyl) -9-ethyl-6- (o-toroil) -9H-carbazole was synthesized by the method described in WO 2009/131189. ..

[Preparation of coloring composition]
The triarylmethane compound A obtained in Synthesis Example 1 and the resins A and B obtained in Synthesis Examples 2 and 3 are mixed with other components so as to have the compositions shown in Table 1 below. A coloring composition was prepared.
The numerical values in the upper row of Table 1 represent the content ratio (mass%) of each component to be added in the coloring composition, and the numerical values in the lower row represent the content ratio (mass%) of each component in the total solid content. show.
At the time of mixing, the mixture was stirred for 1 hour or more until each component was sufficiently mixed, and finally filtered through a 5 μm coma-type filter to remove foreign substances.
Dispersants A to D were used as the dispersants (b) in the coloring compositions of Examples 1 to 4, and dispersants E were used in the coloring compositions of Comparative Example 1.

Each compound in Table 12 is as follows.
DISPERBYK-167: Made by Big Chemie. A dispersant containing an imidazole ring as an adsorbent. Solid amine value is 24 mgKOH / g. A solution having a solid content concentration of 52% by mass.
DISPERBYK-161: Made by Big Chemie. A dispersant containing an imidazole ring as an adsorbent. The solid amine value is 37 mgKOH / g. A solution having a solid content concentration of 30% by mass.

EFKA4046: Made by BASF. A dispersant containing an imidazole ring as an adsorbent. The solid amine value is 51 mgKOH / g. A solution having a solid content concentration of 41% by mass.
EFKA4320: Made by BASF. A dispersant containing a pyridine ring as an adsorbent. The solid amine value is 56 mgKOH / g. A solution having a solid content concentration of 50% by mass.
BYK-LPN6919: Made by Big Chemie. A dispersant containing an aliphatic amine as an adsorbent. The solid amine value is 120 mgKOH / g. A solution having a solid content concentration of 60% by mass.

PGMEA: Propylene glycol monomethyl ether acetate PGME: Propylene glycol monomethyl ether F559: Perfluoroalkyl group-containing oligomer (manufactured by DIC)
Irganox 1010: Pentaerythritol tetrakis [3- (3,5-ditert-butyl-4-hydroxyphenyl) propinate] (manufactured by BASF)
JPP-100: Tetraphenyl Dipropylene Glycol Diphos Fight (manufactured by Johoku Chemical Industry Co., Ltd.)

[Manufacturing of colored cured film and evaluation of heat resistance]
On a glass substrate cut into 5 cm squares, each coloring composition prepared in the above [Preparation of coloring composition] is applied by a spin coating method so that the film thickness after firing is 1.5 μm, and dried under reduced pressure. After that, it was prebaked on a hot plate at 80 ° C. for 3 minutes. Then, after full exposure at an exposure amount of 60 mJ / cm ² , it was fired in a clean oven at 230 ° C. for 30 minutes to obtain a colored cured film. The absorbance of the obtained colored cured film was measured with a spectrophotometer U-3310 (manufactured by Hitachi, Ltd.), the absorption maximums of the absorption spectra were compared, and the absorbance ratio was calculated as the absorbance after firing / the absorbance before firing x 100. bottom. The results are shown in Table 2.

As shown in Table 2, Examples 1 to 4 using a dispersant having an adsorbing group containing an aromatic heterocycle by firing at 230 ° C. for 30 minutes show a maximum absorption due to decomposition of the triarylmethane compound. The decrease in absorbance was suppressed, and the absorbance was equivalent to that of Reference Example 1 in which no dispersant was used. On the other hand, in Comparative Example 1 in which a dispersant having an aliphatic amine was used, it was clarified that the absorbance at the maximum absorption due to the decomposition of the triarylmethane compound was significantly reduced.

When a dispersant having an aliphatic amine is used, the strongly basic aliphatic amine binds to the sp2 carbon located at the center of the three aryl groups of the triarylmethane compound by heating, and the conjugated system collapses and fades. Therefore, it is considered that the absorbance at the maximum absorption was greatly reduced.
On the other hand, when a dispersant having an aromatic heterocycle is used, the weakly basic aromatic heterocycle is less likely to bond with the sp2 carbon of the triarylmethane compound even when heated, and the conjugated system is less likely to collapse and fade. Therefore, it is considered that the decrease in absorbance at the maximum absorption was suppressed.

Further, by using the coloring composition of the present invention, even when a coloring composition containing a solvent-insoluble component, for example, a pigment is used, the pigment can be obtained without deteriorating the heat resistance of the triarylmethane compound. It was suggested that it was well dispersible.

From these results, it is shown that the coloring composition of the present invention satisfies the heat resistance required for the color display manufacturing process.

100 Organic EL element 10 Transparent support substrate 20 pixels 30 Organic protective layer 40 Inorganic oxide film 50 Transparent anode

Claims (7)

A coloring composition containing (a) a colorant, (b) a dispersant, and (c) a solvent.
The colorant (a) contains a triarylmethane-based compound and contains.
The dispersant (b) contains a dispersant (b1) having an adsorbing group containing an aromatic heterocycle.
A coloring composition, wherein the triarylmethane-based compound is a compound represented by the following general formula (I).

In the formula (I), R ^{1 to} R ⁴ independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
Ar represents a monovalent aromatic ring group which may have a substituent.
n represents 0 or 1, and when it is 0, there is no bond.
X represents an a-valent linking group.
A ^c- is a c-valent, represent an halogenoalkyl imide Ani <br/> on- have a substituent.
a, b, c, and d represent integers 1 to 4, and satisfy the relationship of a × b = c × d.
m represents 0 or 1. When m is 0, there is no bond and a is 1. ) The coloring composition according to claim 1, wherein the aromatic heterocycle contained in the adsorbing group of the dispersant (b1) is an imidazole ring, a pyridine ring, or a carbazole ring. The coloring composition according to claim 1 or 2, wherein the colorant (a) further contains a pigment. The coloring composition according to any one of claims 1 to 3, further comprising (d) a binder resin. The coloring composition according to any one of claims 1 to 4, further containing (e) a photopolymerizable monomer and (f) a photopolymerization initiator. A cured product composed of the coloring composition according to any one of claims 1 to 5. An image display device having the cured product according to claim 6.

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